Shading Process

ABSTRACT

The present invention relates to a shading process characterized by using a composition comprising a phthalocyanine to which at least one dyestuff is attached through a covalent bonding, to shading compositions, to new compounds used in these shading compositions as well as to the production of these new compounds.

The present invention relates to a shading process, to shadingcompositions, to new compounds used in these shading compositions aswell as to the production of these new compounds.

A frequently employed method in bleaching and whitening is to use violetor blue dyes concurrently in order to improve the bleaching andwhitening effect. If such a dye is used in conjunction with afluorescent whitening agent, this can serve two different purposes. Onone hand, it is possible to try to achieve an increase in the degree ofwhiteness by compensating for the yellow of the fabric, in which casethe white shade produced by the fluorescent whitening agent on thefabric is largely retained. On the other hand, the object can be toeffect with the dye in question a change in the shade of the whiteeffect produced by the fluorescent whitening agent on the fabric, inwhich case too an attempt is made additionally to achieve an increase inthe degree of whiteness. It is thus possible to adjust the desired shadeof the white effect.

Shading processes of materials such as paper and textile fabrics areknown from e.g. DE 3125495.

These disclosed shading processes use a mixture of a photocatalyst and adyestuff. These disclosed mixtures of photocatalyst and dyestuff are notsuitable for a regular use, such as in detergent or softenerformulations, because the dyestuffs do accumulate with every use andafter a few uses the fabrics are colored. The shading compounds as usedin the present invention do not (or only very slightly) color thetextile fiber material, even if the textile fiber material is treatedrepeatedly with the present inventive shading compostions.

Additionally, the use of a mixture of two components always requires theproper ratio of the two components.

Furthermore, the new shading process using compounds, wherein at leastone dyestuff is attached through a covalent bonding to thephthalocyanine has also an improved exhaustion onto the fabrics, animproved shade substantivity on fabrics and an improved shadeconsistency on exposure to light. Further more the new compounds aremore efficient photocatalyst by additional light absorption and energytransfer to the phthalocyanine part of the molecule.

Therefore, the present invention relates to a shading process fortextile fiber material, wherein the textile fiber material is treatedwith a composition comprising at least one Zn-, Ca-, Mg-, Na-, K-, Al,Si-, Ti-, Ge-, Ga-, Zr-, In- or Sn-phthalocyanine to which at least onedyestuff is attached through a covalent bonding.

A preferred embodiment of the present invention relates to a shadingprocess for textile fiber material, wherein the textile fiber materialis treated with a composition comprising at least one compound offormula (1a) and/or formula (1b)

in which

-   PC is the phthalocyanine ring system,-   Me is Zn; Ca; Mg; Na; K; Al-Z₁; Si(IV)-(Z₁)₂; Ti(IV)-(Z₁)₂;    Ge(IV)-(Z₁)₂; Ga(III)-Z₁; Zr(IV)-(Z₁)₂; In(III)-Z₁ or Sn(IV)-(Z₁)₂,-   Z₁ is an alkanolate ion; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆    ⁻; R₀SO₃ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻; citrate ion; tartrate    ion or oxalate ion, wherein R₀ is hydrogen; or unsubstituted    C₁-C₁₈alkyl; or C₁-C₁₈alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    carboxyl, —SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy, phenyl,    naphthyl and pyridyl; unsubstituted aryl or aryl, which is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, carboxyl, —SO₃H, —NH₂,    carb-C₁-C₆alkoxy, C₁-C₆alkoxy and C₁-C₄-alkyl,-   r is 0; 1; 2; 3 or 4,-   r′ is 1; 2; 3 or 4,-   each Q₁ is independently of each other a sulfo or carboxyl group or    a radical of the formula —SO₂X₂—R₁—X₃ ⁺; —O—R₁—X₃ ⁺ or —(CH₂)_(t)—Y₁    ⁺,    -   in which    -   R₁ is a branched or unbranched C₁-C₈alkylene; 1,3-phenylene or        1,4-phenylene,    -   X₂ is —NH— or —N(C₁-C₅alkyl)-,    -   X₃ ⁺ is a group of the formula

-   -   or, in the case where R₁=C₁-C₈alkylene, also a group of the        formula

-   -   Y₁ ⁺ is a group of the formula

-   -   t is 0 or 1,    -   wherein the above formulae    -   R₂ and R₃ independently of one another are C₁-C₆alkyl,    -   R₄ is C₁-C₆alkyl; C₅-C₇cycloalkyl or NR₇R₈,    -   R₅ and R₆ independently of one another are C₁-C₅alkyl,    -   R₇ and R₈ independently of one another are hydrogen or        C₁-C₅alkyl,    -   R₉ and R₁₀ independently of one another are unsubstituted        C₁-C₆alkyl or C₁-C₆alkyl substituted by at least one substituent        chosen from the group consisting of hydroxyl, cyano, carboxyl,        —SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy, phenyl, naphthyl and        pyridyl,    -   u is from 1 to 6,    -   A₁ is a unit which completes an aromatic 5- to 7-membered        nitrogen heterocycle, which may where appropriate also contain        one or two further nitrogen atoms as ring members, and    -   B₁ is a unit which completes a saturated 5- to 7-membered        nitrogen heterocycle, which may where appropriate also contain 1        to 2 nitrogen, oxygen and/or sulfur atoms as ring members,

-   each Q′ is independently from each other a moiety of formula -L-D,    -   wherein L is a direct bond or a bridging group and    -   D is the radical of a dyestuff,

-   each Q₂ is independently from each other hydroxyl; C₁-C₂₂alkyl;    branched C₃-C₂₂alkyl; C₂-C₂₂alkenyl; branched C₃-C₂₂alkenyl and    mixtures thereof; C₁-C₂₂alkoxy; a sulfo or carboxyl radical; a    radical of the formula

-    a branched alkoxy radical of the formula

an alkylethyleneoxy unit of the formula-(T₁)_(d)-(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of the formula COOR₁₈,

-   -   in which    -   B₂ is hydrogen; hydroxyl; C₁-C₃₀alkyl; C₁-C₃₀alkoxy; —CO₂H;        —CH₂COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁; —PO₃ ²⁻M₁; —OPO₃ ²⁻M₁; and        mixtures thereof,    -   B₃ is hydrogen; hydroxyl; —COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁ or        C₁-C₆alkoxy,    -   M₁ is a water-soluble cation,    -   T₁ is —O— or —NH—,    -   X₁ and X₄ independently of one another are —O—; —NH— or        —N(C₁-C₅alkyl)-,    -   R₁₁ and R₁₂ independently of one another are hydrogen; a sulfo        group and salts thereof; a carboxyl group and salts thereof or a        hydroxyl group; at least one of the radicals R₁₁ and R₁₂ being a        sulfo or carboxyl group or salts thereof,    -   Y₂ is —O—; —S—; —NH— or —N(C₁-C₅alkyl)-,    -   R₁₃ and R₁₄ independently of one another other are hydrogen;        C₁-C₆alkyl; hydroxy-C₁-C₆alkyl; cyano-C₁-C₆alkyl;        sulfo-C₁-C₆alkyl; carboxy or halo-C₁-C₆alkyl; unsubstituted        phenyl or phenyl substituted by at least one substituent chosen        from the group consisting of halogen, C₁-C₄alkyl, C₁-C₄alkoxy,        sulfo or by carboxy; or R₁₈ and R₁₉, together with the nitrogen        atom to which they are bonded, form a saturated 5- or 6-membered        heterocyclic ring that may in addition contain a further        nitrogen atom or an oxygen atom as ring member,    -   R₁₅ and R₁₆ independently of one another are C₁-C₆alkyl or        aryl-C₁-C₆alkyl radicals,    -   R₁₇ is hydrogen; an unsubstituted C₁-C₆alkyl or C₁-C₆alkyl        substituted by at least one substituent chosen from the group        consisting of halogen, hydroxyl, cyano, SO₃H, —NH₂, phenyl,        carboxyl, carb-C₁-C₆alkoxy and C₁-C₆alkoxy,    -   R₁₈ is C₁-C₂₂alkyl; branched C₃-C₂₂alkyl; C₁-C₂alkenyl or        branched C₃-C₂₂alkenyl; C₃-C₂₂glycol; C₁-C₂₂alkoxy; branched        C₃-C₂₂alkoxy; and mixtures thereof,    -   M is hydrogen; or an alkali metal ion or ammonium ion,    -   Z₂ is a is an alkanolate ion; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻;        BF₄ ⁻; PF₆ ⁻; R₀SO₃ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻; citrate        ion; tartrate ion or oxalate ion, wherein R₀ is hydrogen; or        unsubstituted C₁-C₁₈alkyl; or C₁-C₁₈alkyl, which is substituted        by at least one substituent chosen from the group consisting of        hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy,        C₁-C₆alkoxy, phenyl, naphthyl and pyridyl; unsubstituted aryl or        aryl, which is substituted by at least one substituent chosen        from the group consisting of hydroxyl, cyano, carboxyl, —SO₃H,        —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy and C₁-C₄-alkyl,    -   a is 0 or 1,    -   b is from 0 to 6,    -   c is from 0 to 100,    -   d is 0 or 1,    -   e is from 0 to 22,    -   v is an integer from 2 to 12,    -   w is 0 or 1, and

-   A⁻ is an organic or inorganic anion, and    -   s is equal to r in cases of monovalent anions A⁻ and is ≦r in        cases of polyvalent anions, it being necessary for A_(s) ⁻ to        compensate the positive charge; where, when r≠1, the radicals Q₁        can be identical or different,        and where the phthalocyanine ring system may also comprise        further solubilising groups.

The composition comprising at least one compound of formula (1a) and/or(1b) produces a relative hue angle of 220-320° and the compounds offormula (1a) and (1b) are not light stable. That means that thecompounds of formula (1a) and/or (1b) of the shading composition aredestroyed by light. Visible light (400 to 800 nm) is meant by the term“light”. Preferably, it is sunlight.

Color coordinates and color differences are expressed using theinternationally standardized CIELAB tristimulus values:

a*=red−green (+, −)b*=yellow−blue (+, −)L*=lightness (light=100)C*=chromaH*=hue (angle of 0°=red, 90°=yellow, 180°=green, 270°=blue),and the color differences ΔE*, ΔH*, ΔC*, ΔL*, Δa*, and Δb*, togetherwith an identification number of the sample.

This internationally accepted system has been developed by CIE(“Commission Internationale de l'Eclairage”). It is for example part ofDIN 6174: 1979-01 as well as DIN 5033-3: 1992-07.

The composition comprising at least one compound of formula (1a) and/or(1b) produces a relative hue angle of 220-320° and the compounds offormula (1a) and (1b) are degraded when the composition is exposed tosunlight. Preferably, the compounds of formula (1a) and (1b) aredestroyed by light, preferably sunlight, when they are applied onto thetextile fiber material.

The composition comprising at least one compound of formula (1a) and/or(1b) produces a relative hue angle of 220-320° and the decrease rate ofthe compounds of formula (1a) and/or (1b) is at least 1% per 2 hours,preferably at least 2% when the composition is exposed to (sun)light.Preferably, the compounds of formula (1a) and (1b) are destroyed bylight, preferably sunlight, when they are applied onto the textile fibermaterial and the decrease rate of compounds of formula (1a) and/or (1b)is at least 1% per 2 hours, preferably at least 2%.

For example, the degradation of the components can be determinedspectrophotometrically.

Preferably, the degradation of the compound of formula (1a) and formula(1b) when applied onto the textile fiber material does not change thecolor of the textile fiber material, even if the textile fiber materialis treated with these compounds repeatedly.

Examples of suitable textile fiber materials are materials made of silk,wool, polyamide, acrylics or polyurethanes, and, in particular,cellulosic fiber materials and blends of all types. Such fiber materialsare, for example, natural cellulose fibers, such as cotton, linen, juteand hemp, and regenerated cellulose. Preference is given to textilefiber materials made of cotton. Also suitable are hydroxyl-containingfibers which are present in mixed fabrics, for example mixtures ofcotton with polyester fibers or polyamide fibers.

Halogen means fluorine, bromine or, in particular, chlorine.

Especially suitable groups

in the formulae (1a) and (1b) are:

Preference is given to the group

Suitable heterocyclic rings in the group

are likewise the groups listed above, the bond to the other substituentsmerely being via a carbon atom.

In all of these substituents, phenyl, naphthyl and aromatic hetero ringsmay be substituted by one or two further radicals, for example byC₁-C₆alkyl, C₁-C₆alkoxy, halogen, carboxyl, carb-C₁-C₆alkoxy, hydroxyl,amino, cyano, sulfo, sulfonamido, etc.

Preference is given to a substituent from the group C₁-C₆alkyl,C₁-C₆alkoxy, halogen, carboxyl, carb-C₁-C₆alkoxy or hydroxyl.

Particularly suitable groups

are:

etc, whereinB₁ and R₆ have the same meaning as defined above.

All of the aforementioned nitrogen heterocycles can also be substitutedby alkyl groups, either on a carbon atom or on another nitrogen atom inthe ring. The alkyl group is preferably the methyl group.

A⁻ _(s) n formula (1a) is, as a counterion to the positive charge on theremainder of the molecule, any anion. In general, it is introduced bythe preparation process (quaternization). It is then preferably a is analkanolate ion; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; R₀SO₃ ⁻;SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻; citrate ion; tartrate ion or oxalateion, wherein R₀ is hydrogen; or unsubstituted C₁-C₁₈alkyl; orC₁-C₁₈alkyl, which is substituted by at least one substituent chosenfrom the group consisting of hydroxyl, cyano, carboxyl, —SO₃H, —NH₂,carb-C₁-C₆alkoxy, C₁-C₆alkoxy, phenyl, naphthyl and pyridyl;unsubstituted aryl or aryl, which is substituted by at least onesubstituent chosen from the group consisting of hydroxyl, cyano,carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy and C₁-C₄-alkyl.Arylsulfate ions which may be mentioned are the phenylsulfonate,p-tolylsulfonate and the p-chlorophenylsulfonate ion. The anion canhowever also be any other anion since the anions can be readilyexchanged in a known manner; A_(s) ⁻ can thus also be a sulfate,sulfite, carbonate, phosphate, nitrate, acetate, oxalate, citrate,lactate ion or another anion of an organic carboxylic acid. The index sis the same as r for monovalent anions. For polyvalent anions, s has avalue ≦r, in which case it must be chosen, depending on the conditions,such that it exactly balances the positive charge on the remainder ofthe molecule.

C₁-C₆alkyl and C₁-C₆alkoxy are straight-chain or branched alkyl oralkoxy radicals, such as, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl orhexyl or methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy,tert-butoxy, amyloxy, isoamyloxy, tert-amyloxy or hexyloxy.

C₂-C₂₂alkenyl is, for example, allyl, methallyl, isopropenyl, 2-butenyl,3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl,n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl orn-octadec-4-enyl.

Preferably, Me is Zn, AlZ₁, Si(IV)-(Z₁)₂ or Ti(IV)-(Z₁)₂, wherein Z₁ hasthe meanings as defined above.

More preferably, Me is Zn, AlZ₁, Si(IV)-(Z₁)₂ or Ti(IV)-(Z₁)₂, whereinZ₁ is chloride, fluorine, bromine or hydroxyl.

Preferably, the sum of r and r′ is from 2 to 6, more preferably the sumis 4.

Preferably, R₁ is a branched or unbranched C₁-C₄alkylene; or 1,3- or1,4-phenylene.

Preferably, X₂ is —NH— or —N(C₁-C₄alkyl)-.

Preferably, R₂ and R₃ independently of one another are C₁-C₄alkyl.

Preferably, R₄ is C₁-C₄alkyl; pentyl; hexyl or NR₇R₈.

Preferably, R₅ and R₆ independently of one another are C₁-C₄alkyl.

Preferably, R₇ and R₈ independently of one another are hydrogen orC₁-C₄alkyl.

Preferably, R₉ and R₁₀ independently of one another are unsubstitutedC₁-C₄alkyl or C₁-C₄alkyl, which is substituted by at least onesubstituent chosen from the group consisting of hydroxyl, cyano, SO₃H,—NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl andpyridyl.

Preferably, u is 1; 2; 3 or 4.

Preferably, A₁ is a unit which completes an pyrrole-; imidazol-;pyridine-; pyrazine-; pyrimidine- or pyridazine-ring.

Preferably, B₁ is a unit which completes a morpholino-; pyrrolidine-;piperazine- or piperidine-ring.

Preferably, L is a direct bond; —SO₂—; —(CH₂)₁₋₄—SO₂—; —O—;—(CH₂)₁₋₄—O—; —OR₁₉—; —(CH₂)₁₋₄—OR₁₉—; —OR₁₉O—; —(CH₂)₁₋₄—OR₁₉O—;—OR₁₉N(R₂₀)—; —(CH₂)₁₋₄—OR₁₉N(R₂₀)—; —N(R₂₀)—; —(CH₂)₁₋₄—N(R₂₀)——(CH₂CH₂O—)_(n)—; —C(O)—; —(CH₂)₁₋₄—C(O)—; —C(O)N(R₂₀)—;—(CH₂)₁₋₄—C(O)N(R₂₀)—; —N(R₂₀)C(O)—; —(CH₂)₁₋₄—N(R₂₀)C(O)—; —OC(O)—;—(CH₂)₁₋₄—OC(O)—; —C(O)O—; —(CH₂)₁₋₄—C(O)O—; —S—; —(CH₂)₁₋₄—S—;unsubstituted, linear or branched C₁-C₁₈alkylene;

-   -   linear or branched C₁-C₁₈alkylene, which is substituted by at        least one substituent chosen from the group consisting of        hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy,        C₁-C₄alkoxy, phenyl, naphthyl and pyridyl;    -   unsubstituted C₅-C₁₈arylene;    -   C₅-C₁₈arylene, which is substituted by at least one substituent        chosen from the group consisting of hydroxyl, cyano, carboxyl,        carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl;    -   unsubstituted, linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl;    -   linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl, which is        substituted by at least one substituent chosen from the group        consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,        carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and        pyridyl;    -   unsubstituted, linear or branched C₅-C₁₈arylene-C₁-C₁₈alkyl or        linear or branched C₅-C₁₈arylene-C₁-C₁₈alkyl, which is        substituted by at least one substituent chosen from the group        consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,        carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and        pyridyl, wherein        -   R₁₉ is unsubstituted, linear or branched C₁-C₁₈alkylene;            linear or branched C₁-C₁₈alkylene, which is substituted by            at least one substituent chosen from the group consisting of            hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy,            C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; unsubstituted            C₅-C₁₈arylene; C₅-C₁₈arylene, which is substituted by at            least one substituent chosen from the group consisting of            hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy,            C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted, linear or            branched C₁-C₁₈alkylene-C₅-C₁₈aryl; linear or branched            C₁-C₁₈alkylene-C₅-C₁₈aryl, which is substituted by at least            one substituent chosen from the group consisting of            hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy,            C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl;            unsubstituted, linear or branched C₅-C₁₈arylene-C₁-C₁₈alkyl            or linear or branched C₅-C₁₈arylene-C₁-C₁₈alkyl, which is            substituted by at least one substituent chosen from the            group consisting of hydroxyl, cyano, carboxyl,            carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl            and pyridyl,        -   R₂₀ is unsubstituted, linear or branched C₁-C₁₈alkyl; linear            or branched C₁-C₁₈alkyl, which is substituted by at least            one substituent chosen from the group consisting of            hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy,            C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; unsubstituted            C₅-C₁₈aryl; C₅-C₁₈aryl, which is substituted by at least one            substituent chosen from the group consisting of hydroxyl,            cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy            and C₁-C₄alkyl; unsubstituted, linear or branched            C₁-C₁₈alkoxy or linear or branched C₁-C₁₈alkoxy, which is            substituted by at least one substituent chosen from the            group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,            carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl,    -   n is 1; 2; 3 or 4,

Preferably, D is the radical of a azo- (such as for example acid violetdyes); diazo-; trisazo-, polyazo-; azomethin-; methin-; anthrachino-;dioxazine-; phenazine-; diphenylmethane-; triphenylmethane-; carbonyl-;xanthene-; acid- or thioxanthene-dyestuff.

Preferably, B₂ is hydrogen; hydroxyl; C₁-C₁₈alkyl; C₁-C₁₈alkoxy; —CO₂H;—CH₂COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁; —PO₃ ²⁻M₁; —OPO₃ ²⁻M₁; and mixturesthereof, wherein M₁ has the meanings as defined above.

Preferably, B₃ is hydrogen; hydroxyl; —COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁ orC₁-C₄alkoxy.

Preferably, M₁ is hydrogen; alkalimetal-ion or an ammonium ion.

Preferably, X₁ and X₄ independently of one another are —O—; —NH— or—N(C₁-C₄alkyl)-.

Preferably, Y₂ is —O—; —S—; —NH— or —N(C₁-C₄alkyl)-.

Preferably, R₁₃ and R₁₄ independently of one another are hydrogen;C₁-C₄alkyl; hydroxy-C₁-C₄alkyl; cyano-C₁-C₄alkyl; sulfo-C₁-C₄alkyl;carboxy or halogen-C₁-C₄alkyl; unsubstituted phenyl or phenylsubstituted by at least one substitutent chosen from the groupconsisting of halogen, C₁-C₄alkyl or C₁-C₄alkoxy; sulfo and carboxyl; orR₁₃ and R₁₄ together with the nitrogen atom to which they are bondedform a form morpholino, piperazine or piperidine ring.

Preferably, R₁₅ and R₁₆ independently of one another are C₁-C₄alkyl oraryl-C₁-C₄alkyl radicals.

Preferably, R₁₇ is hydrogen; an unsubstituted C₁-C₄alkyl or C₁-C₄alkylsubstituted at least one substituent chosen from the group consisting ofhalogen, hydroxyl, cyano, —SO₃H, —NH₂, phenyl, carboxyl,carb-C₁-C₄alkoxy and C₁-C₆alkoxy.

Preferably, R₁₈ is C₁-C₁₀alkyl; branched C₃-C₁₀alkyl; C₁-C₁₀alkenyl orbranched C₃-C₁₀alkenyl; C₃-C₂₂glycol; C₁-C₁₀alkoxy; branchedC₃-C₁₀alkoxy; and mixtures thereof.

Preferably, M is hydrogen; Na⁺; K⁺ or an ammonium ion.

Preferably, Z₂ ⁻ is a chlorine; bromine; alkylsulfate or aralkylsulfateion.

Preferably, a is 0 or 1.

Preferably, b is from 0 to 6.

Preferably, c is from 0 to 100.

Preferably, d is 0 or 1.

Preferably, e is from 0 to 22.

Preferably, v is an integer from 2 to 12.

Preferably, w is 0 or 1.

Preferably, A⁻ halogen ion; an alkyl sulfate ion; an aryl sulfate ion;sulfate, sulfite, carbonate, phosphate, nitrate, acetate, oxalate,citrate or lactate ion or another anion of an organic carboxylic acid.

Preferred dyestuff radicals D have the following formulae (I)-(XXXII):

wherein

-   * marks the bond to the bridging group L,-   X and Y independently of one another, are hydrogen; SO₃M; linear or    branched, unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl,    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear    or branched, unsubstituted C₁-C₄-alkoxy; linear or branched,    C₁-C₄-alkoxy, which is substituted by at least one substituent    chosen from the group consisting of hydroxyl, cyano, SO₃H, —NH₂,    carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and    pyridyl; NHCOOH; NHCOOC₁-C₄alkyl; COOH or COOC₁-C₄alkyl;-   U is a moiety of formula

-   R_(α) is hydrogen; linear or branched, unsubstituted C₁-C₄-alkyl;    linear or branched C₁-C₄-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,    naphthyl and pyridyl; unsubstituted aryl or aryl, which is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl,-   each R_(β) independently of one another is hydrogen; SO₃M; linear or    branched, unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl,    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear    or branched, unsubstituted C₁-C₄-alkoxy or linear or branched,    C₁-C₄-alkoxy, which is substituted by at least one substituent    chosen from the group consisting of hydroxyl, cyano, SO₃H, —NH₂,    carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and    pyridyl,-   Z is linear or branched, unsubstituted C₁-C₄-alkyl; linear or    branched C₁-C₄-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy    or linear or branched, C₁-C₄-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; halogen; OH; NO₂; COOH; COOC₁-C₄alkyl; NH₂;    NHC₁-C₄alkyl, wherein the alkyl group may be substituted by at least    one substituent chosen from the group consisting of OH, NH₂,    C₁-C₄alkyl, CN and COOH; N(C₁-C₄alkyl)C₁-C₄alkyl, wherein the alkyl    groups may independently of each other be substituted by at least    one substituent chosen from the group consisting of OH, NH₂,    C₁-C₄alkyl, CN and COOH; NH-aryl; NH-aryl,

wherein the aryl is substituted by at least one substituent chosen fromthe group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,carb-C₁-C₄alkoxy, C₁-C₄alkyl and C₁-C₄alkoxy; NHCOC₁-C₄alkyl andNHCOOC₁-C₄alkyl,

-   Z₁ is SO₃M; linear or branched, unsubstituted C₁-C₄-alkyl; linear or    branched C₁-C₄-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy    or linear or branched, C₁-C₄-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; halogen; OH; NO₂; COOH; COOC₁-C₄alkyl; NH₂;    NHC₁-C₄alkyl, wherein the alkyl group may be substituted by at least    one substituent chosen from the group consisting of OH, NH₂,    C₁-C₄alkyl, CN or COOH; N(C₁-C₄alkyl)C₁-C₄alkyl, wherein the alkyl    groups may independently of each other be substituted by at least    one substituent chosen from the group consisting of OH, NH₂,    C₁-C₄alkyl, CN and COOH; NH-aryl; NH-aryl, wherein the aryl is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkyl and C₁-C₄alkoxy; NHCOC₁-C₄alkyl or    NHCOOC₁-C₄alkyl,-   Z₁ is linear or branched, unsubstituted C₁-C₄-alkyl; linear or    branched C₁-C₄-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy    or linear or branched, C₁-C₄-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; halogen; OH; NO₂; COOH; COOC₁-C₄alkyl; NH₂;    NHC₁-C₄alkyl, wherein the alkyl group may be substituted by at least    one substituent chosen from the group consisting of OH, NH₂,    C₁-C₄alkyl, CN or COOH; N(C₁-C₄alkyl)C₁-C₄alkyl, wherein the alkyl    groups may independently of each other be substituted by at least    one substituent chosen from the group consisting of OH, NH₂,    C₁-C₄alkyl, CN and COOH; NH-aryl; NH-aryl, wherein the aryl is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkyl and C₁-C₄alkoxy; NHCOC₁-C₄alkyl or    NHCOOC₁-C₄alkyl,    wherein-   * marks the bond to the bridging group L,-   Z is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; or NO₂,-   Z₁ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; or NO₂,-   Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; NH₂; or NO₂,-   Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; or NO₂,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one-   Z₂, Z₃, Z₄, Z₅ and Z₆ are independently from each other hydrogen;    linear or branched, unsubstituted C₁-C₄-alkyl; linear or branched    C₁-C₄-alkyl, which is substituted by at least one substituent chosen    from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear    or branched, unsubstituted C₁-C₄-alkoxy or linear or branched,    C₁-C₄-alkoxy, which is substituted by at least one substituent    chosen from the group consisting of hydroxyl, cyano, SO₃H, —NH₂,    carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and    pyridyl; halogen; OH; SO₂CH₂CH₂SO₃H; NO₂; COOH; COOC₁-C₄alkyl; NH₂;    NHC₁-C₄alkyl, wherein the alkyl group may be substituted by at least    one substituent chosen from the group consisting of OH, NH₂,    C₁-C₄alkyl, CN or COOH; N(C₁-C₄alkyl)C₁-C₄alkyl, wherein the alkyl    groups may independently of each other be substituted by at least    one substituent chosen from the group consisting of OH, NH₂,    C₁-C₄alkyl, CN and COOH; NH-aryl; NH-aryl, wherein the aryl is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkyl and C₁-C₄alkoxy; NHCOC₁-C₄alkyl or    NHCOOC₁-C₄alkyl,-   G is a direct bond; COOC₁-C₄alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted    C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and    C₁-C₄alkyl; or —CO-arylene,-   n is 0; 1; 2 or 3,-   n′ is 0; 1 or 2,-   n″ is 0 or 1,-   m is 0; 1 or 2,-   m₁ is 0; 1 or 2,-   each M is independently from each other hydrogen; an alkali metal    ion or an ammonium ion.

More preferred dyestuff radicals D have the following formulae(I′)-(XXXII′):

wherein

-   X and Y independently of one another are linear or branched,    unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl, which is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear    or branched, unsubstituted C₁-C₄-alkoxy,-   Z is unsubstituted C₁-C₂-alkyl; C₁-C₂-alkyl, which is substituted by    at least one substituent chosen from the group consisting of    hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,    C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,    unsubstituted C₁-C₄-alkoxy; OH; NO₂; COOH; COOC₁-C₂alkyl,-   Z₁ is halogen; OH; NO₂; COOH or COOC₁-C₄alkyl,-   G is a direct bond; unsubstituted arylene; arylene which is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 0; 1 or 2,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   X and Y independently of one another are linear or branched,    unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl, which is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear    or branched, unsubstituted C₁-C₄-alkoxy,-   Z is unsubstituted C₁-C₂-alkyl; C₁-C₂-alkyl, which is substituted by    at least one substituent chosen from the group consisting of    hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,    C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,    unsubstituted C₁-C₄-alkoxy; OH; NO₂; COOH; COOC₁-C₂alkyl,-   Z₁ is OH; NO₂; COOH or COOC₁-C₂alkyl,-   G is a direct bond; unsubstituted arylene; arylene which is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 0; 1 or 2,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   X and Y independently of one another are linear or branched,    unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl, which is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear    or branched, unsubstituted C₁-C₄-alkoxy,-   Z is unsubstituted C₁-C₂-alkyl; C₁-C₂-alkyl, which is substituted by    at least one substituent chosen from the group consisting of    hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,    C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,    unsubstituted C₁-C₄-alkoxy; OH; NO₂; COOH; COOC₁-C₂alkyl,-   Z₁ is OH; NO₂; COOH or COOC₁-C₄alkyl,-   G is a direct bond; unsubstituted arylene; arylene which is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 0; 1 or 2,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   Z is unsubstituted C₁-C₂-alkyl; C₁-C₂-alkyl, which is substituted by    at least one substituent chosen from the group consisting of    hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,    C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,    unsubstituted C₁-C₄-alkoxy; OH; NO₂; COOH; COOC₁-C₂alkyl,-   Z₁ is OH; NO₂; COOH or COOC₁-C₂alkyl,-   G is a direct bond or COOC₁-C₂alkylene,-   n is 0; 1 or 2,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   Z is unsubstituted C₁-C₂-alkyl; C₁-C₂-alkyl, which is substituted by    at least one substituent chosen from the group consisting of    hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,    C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,    unsubstituted C₁-C₄-alkoxy; OH; NO₂; COOH; COOC₁-C₂alkyl,-   G is a direct bond or COOC₁-C₂alkylene,-   n is 0; 1 or 2,-   n″ is 0 or 1,-   m is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   Z is unsubstituted C₁-C₂-alkyl; C₁-C₂-alkyl, which is substituted by    at least one substituent chosen from the group consisting of    hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy,    C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched,    unsubstituted C₁-C₄-alkoxy; OH; NO₂; COOH; COOC₁-C₂alkyl,-   G is a direct bond or COOC₁-C₂alkylene,-   n is 0; 1 or 2,-   n″ is 0 or 1,-   m is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or    linear or branched, C₁-C₂-alkoxy, which substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂,-   Y is SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or    linear or branched, C₁-C₂-alkoxy, which substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂,-   Z is NH₂ or NHCOOC₁-C₄alkyl,-   Z₁ is OH or NHCOC₁-C₄alkyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and    C₁-C₄alkyl,-   n is 0; 1 or 2,-   n″ is 0 or 1,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or    linear or branched, C₁-C₂-alkoxy, which is substituted by at least    one substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂,-   Y is SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or    linear or branched, C₁-C₂-alkoxy, which is substituted by at least    one substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂,-   Z is NH₂ or NHCOOC₁-C₄alkyl,-   Z₁ is OH or NHCOC₁-C₄alkyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and    C₁-C₄alkyl,-   n is 1; 2 or 3,-   n″ is 0 or 1,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or    linear or branched, C₁-C₂-alkoxy, which is substituted by at least    one substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂,-   Y is SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or    linear or branched, C₁-C₂-alkoxy, which is substituted by at least    one substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂,-   Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of SO₃H,    carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and C₁-C₂alkoxy,-   Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 1; 2 or 3,-   n″ is 0 or 1,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or    linear or branched, C₁-C₂-alkoxy, which is substituted by at least    one substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂,-   Y is SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or    linear or branched, C₁-C₂-alkoxy, which is substituted by at least    one substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂,-   Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of SO₃H,    carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and C₁-C₂alkoxy,-   Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 1; 2 or 3,-   n″ is 0 or 1,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   Z is NH₂; NHCOC₁-C₄alkyl or NHCOOC₁-C₄alkyl,-   Z₁ is OH; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl and    C₁-C₄alkoxy,-   G is a direct bond; COOC₁-C₄alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted    C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and    C₁-C₄alkyl,-   n is 1; 2 or 3,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   Z is NH₂; NHCOC₁-C₄alkyl or NHCOOC₁-C₄alkyl,-   Z₁ is OH; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl and    C₁-C₄alkoxy,-   G is a direct bond; COOC₁-C₄alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted    C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and    C₁-C₄alkyl,-   n is 1; 2 or 3,-   n″ is 0 or 1,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   Z is NH₂; NHCOC₁-C₄alkyl or NHCOOC₁-C₄alkyl,-   Z₁ is OH; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl and    C₁-C₄alkoxy,-   G is a direct bond; COOC₁-C₄alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted    C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and    C₁-C₄alkyl,-   n is 1; 2 or 3,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or    linear or branched, C₁-C₂-alkoxy, which is substituted by at least    one substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂,-   Y is SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or    linear or branched, C₁-C₂-alkoxy, which is substituted by at least    one substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H and —NH₂,-   Z is NH₂; NHCOC₁-C₄alkyl or NHCOOC₁-C₄alkyl,-   Z₁ is OH; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl and    C₁-C₄alkoxy,-   G is a direct bond; COOC₁-C₄alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted    C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and    C₁-C₄alkyl,

n is 1; 2 or 3,

m is 0 or 1,

m₁ is 0 or 1,

-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₄-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted    C₁-C₄-alkoxy; linear or branched, C₁-C₄-alkoxy, which is substituted    by at least one substituent chosen from the group consisting of    hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl,    phenyl, naphthyl and pyridyl; COOH or COOC₁-C₂alkyl,-   Y is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₄-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted    C₁-C₄-alkoxy; linear or branched, C₁-C₄-alkoxy, which is substituted    by at least one substituent chosen from the group consisting of    hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl,    phenyl, naphthyl and pyridyl; COOH or COOC₁-C₂alkyl,-   Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and    C₁-C₂alkoxy,-   Z′ is SO₃M; COOH or COOC₁-C₂alkyl,-   Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 1; 2 or 3,-   n′ is 0 or 1,-   n″ is 0 or 1,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₄-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted    C₁-C₄-alkoxy; linear or branched, C₁-C₄-alkoxy, which is substituted    by at least one substituent chosen from the group consisting of    hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl,    phenyl, naphthyl and pyridyl; COOH or COOC₁-C₂alkyl,-   Y is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₄-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted    C₁-C₄-alkoxy; linear or branched, C₁-C₄-alkoxy, which is substituted    by at least one substituent chosen from the group consisting of    hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl,    phenyl, naphthyl and pyridyl; COOH or COOC₁-C₂alkyl,-   Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and    C₁-C₂alkoxy,-   Z′ is SO₃M; COOH or COOC₁-C₂alkyl,-   Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 1; 2 or 3,-   n′ is 0 or 1,-   n″ is 0 or 1,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₄-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted    C₁-C₄-alkoxy; linear or branched, C₁-C₄-alkoxy, which is substituted    by at least one substituent chosen from the group consisting of    hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl,    phenyl, naphthyl and pyridyl; COOH or COOC₁-C₂alkyl,-   Y is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₄-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted    C₁-C₄-alkoxy; linear or branched, C₁-C₄-alkoxy, which is substituted    by at least one substituent chosen from the group consisting of    hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl,    phenyl, naphthyl and pyridyl; COOH or COOC₁-C₂alkyl,-   Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and    C₁-C₂alkoxy,-   Z′ is SO₃M; COOH or COOC₁-C₂alkyl,-   Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 1; 2 or 3,-   n′ is 0 or 1,-   n″ is 0 or 1,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and    C₁-C₂alkoxy,-   Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 1; 2 or 3,-   n′ is 0 or 1,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and    C₁-C₂alkoxy,-   Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 1; 2 or 3,-   n′ is 0 or 1,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and    C₁-C₂alkoxy,-   Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 1; 2 or 3,-   n′ is 0 or 1,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and    C₁-C₂alkoxy,-   Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 1; 2 or 3,-   n′ is 0 or 1,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺; or

wherein

-   * marks the bond to the bridging group L,-   Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and    C₁-C₂alkoxy,-   Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 1; 2 or 3,-   n′ is 0 or 1,-   m is 0 or 1,-   m₁ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺,

wherein

-   * marks the bond to the bridging group L,-   Z₂ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl,    naphthyl and pyridyl or OH,-   Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl    group may be substituted by at least one substituent chosen from the    group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl    or NHCOOC₁-C₂alkyl,-   Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl    group may be substituted by at least one substituent chosen from the    group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl    or NHCOOC₁-C₂alkyl,-   Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl or    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl,

G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylenewhich is substituted by at least one substituent chosen from the groupconsisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstitutedC₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least onesubstituent chosen from the group consisting of hydroxyl, cyano, NO₂,SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl,

-   n is 0; 1 or 2,-   n′ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   Z₂ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl,    naphthyl and pyridyl or OH,-   Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl    group may be substituted by at least one substituent chosen from the    group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl    or NHCOOC₁-C₂alkyl,-   Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl or    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl,

G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylenewhich is substituted by at least one substituent chosen from the groupconsisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstitutedC₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least onesubstituent chosen from the group consisting of hydroxyl, cyano, NO₂,SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl,

-   n is 1; 2 or 3,-   n′ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   Z₂ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂,-   Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl    group may be substituted by at least one substituent chosen from the    group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl    or NHCOOC₁-C₂alkyl,-   Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl    group may be substituted by at least one substituent chosen from the    group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl    or NHCOOC₁-C₂alkyl,-   Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; NO₂,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   each n is independently from each other 1; 2 or 3,-   each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein

-   * marks the bond to the bridging group L,-   Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; or NO₂,-   Z₄ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; SO₂CH₂CH₂SO₃H; or NO₂,-   Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl    group may be substituted by at least one substituent chosen from the    group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl    or NHCOOC₁-C₂alkyl,-   Z₆ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; or NO₂,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   n is 1 or 2,-   n′ is 0 or 1,-   each M is independently from each other hydrogen; Na⁺ or K⁺,

wherein

-   * marks the bond to the bridging group L,-   Z is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; or NO₂,-   Z₁ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; or NO₂,-   Z₂ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; or NO₂,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   m is 0 or 1,-   m1 is 0 or 1,-   n is 0 or 1,-   each n′ is independently from each other 0; 1 or 2,-   each M is independently from each other hydrogen; Na⁺ or K⁺,

wherein

-   * marks the bond to the bridging group L,-   Z is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; or NO₂,-   Z₁ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; or NO₂,-   Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; or NO₂,-   Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; or NO₂,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   U is a moiety of formula

wherein Z₂ and Z₃ have the meanings as defined above,

-   m is 0 or 1,-   m1 is 0 or 1,-   n is 0 or 1,-   n′ is 0; 1 or 2,-   each M is independently from each other hydrogen; Na⁺ or K⁺,

-    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   U is a moiety of formula

wherein Z₂ and Z₃ have the meanings as defined above,

-   m is 0 or 1,-   m1 is 0 or 1,-   each n is independently from each other 0; 1 or 2,-   each M is independently from each other hydrogen; Na⁺ or K⁺,

wherein

-   * marks the bond to the bridging group L,-   Z is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; NH₂ or NO₂,-   Z₁ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; or NO₂,-   Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; NH₂; or NO₂,-   Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; or NO₂,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   U is a moiety of formula

wherein Z₂ and Z₃ have the meanings as defined above,

-   m is 0 or 1,-   m1 is 0 or 1,-   n is 1; 2 or 3,-   n′ is 0; 1 or 2,-   each M is independently from each other hydrogen; Na⁺ or K⁺,

wherein

-   * marks the bond to the bridging group L,-   Z is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; NH₂ or NO₂,-   Z₁ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or    branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; or NO₂,-   Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; NH₂; or NO₂,-   Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl;    linear or branched C₁-C₂-alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl,    naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy    or linear or branched, C₁-C₂-alkoxy, which is substituted by at    least one substituent chosen from the group consisting of hydroxyl,    cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,    naphthyl and pyridyl; OH; or NO₂,-   G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene    which is substituted by at least one substituent chosen from the    group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl,    carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted    C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and    C₁-C₂alkyl,-   U is a moiety of formula

wherein Z₂ and Z₃ have the meanings as defined above,

-   m is 0 or 1,-   m1 is 0 or 1,-   n is 1; 2 or 3,-   n′ is 0; 1 or 2,-   each M is independently from each other hydrogen; Na⁺ or K⁺.

Especially preferred dyestuff radicals D are those of the followingformulae (XXXIII)-(XXXV):

which is the radical of Direct Red 254.

The mixture of the dyestuff formula (XXXIV) and (XXXV) is known asDirect Violet 99 (trade name: Pontamine Brilliant Violet.)

The following dyestuffs are also suitable:

Preferred photobleaching agents of the formula (1a) have the formula

in which

-   PC, X₂, X₃, R₁, L, D, r₁, r₂ and r′ are as defined above (including    the preferences),-   Me is Zn, AlZ₁, Si(IV)-(Z₁)₂ or Ti(IV)-(Z₁)₂, wherein Z₁ is    chloride, fluorine, bromine or hydroxyl,-   M is hydrogen; an alkali metal ion; ammonium ion or amine salt ion,-   and the sum of the numbers r₁, r₂ and r′ is from 1 to 8 and-   A_(s) ⁻ balances exactly the positive charge on the remainder of the    molecule.

More preferred photobleaching agents of the formula (1a) have theformula

in which

-   PC, L and D are as defined above (including the preferences),-   Me is Zn, AlZ₁, Si(IV)-(Z₁)₂ or Ti(IV)-(Z₁)₂, wherein Z₁ is    chloride, fluorine, bromine or hydroxyl,-   R₁′ is C₂-C₆alkylene,-   r₁ is a number from 0 to 4, preferably 1 to 4,-   r′ is a number from 1 to 4,-   X₃′⁺ is a group of the formula

-   -   in which    -   R₂ and R₃ independently of one another are unsubstituted linear        or branched C₁-C₄alkyl or linear or branched C₁-C₄alkyl        substituted by at least one substituent chosen from the group        consisting of hydroxyl, cyano, halogen and phenyl,    -   R₄ is R₂; cyclohexyl or amino,    -   R₆ is C₁-C₄alkyl,    -   R₁₆ is C₁-C₄alkyl; C₁-C₄alkoxy; halogen; carboxyl;        carb-C₁-C₄alkoxy or hydroxyl, and

-   A′⁻ is a halide; alkylsulfate or arylsulfate ion,    it being possible for the radicals —SO₂NHR′₁—X₃′⁺A′⁻ to be identical    or different.

Other photobleaching agents which can be used according to the inventionhave the formula

in which

-   PC, L and D are as defined above (including the preferences),-   Me is Zn; Ca; Mg; Na; K; Al-Z₁; Si(IV)-(Z₁)₂; Ti(IV)-(Z₁)₂;    Ge(IV)-(Z₁)₂; Ga(III)-Z₁; Zr(IV)-(Z₁)₂; In(III)-Z₁ or Sn(IV)-(Z₁)₂,-   Z₁ is a alkanolate; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻;    R₀SO₃ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻; citrate ion; tartrate ion    or oxalate ion, wherein R₀ is hydrogen; or unsubstituted    C₁-C₁₈alkyl; or C₁-C₁₈alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy, phenyl,    naphthyl and pyridyl; unsubstituted aryl or aryl, which is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂,    carb-C₁-C₆alkoxy, C₁-C₆alkoxy and C₁-C₄-alkyl,-   Y₃′ is hydrogen; an alkali metal ion or ammonium ion, and-   r is any number from 0 to 4, preferably any number from 1 to 4,-   r′ is any number from 1 to 4.

Very particularly preferred phthalocyanine compounds have the formula(4a),

in which

-   PC, L and D are as defined above (including the preferences),-   Me is Zn or Al-Z₁,-   Z₁ is a alkanolate; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻;    R₀SO₃ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻; citrate ion; tartrate ion    or oxalate ion, wherein R₀ is hydrogen; or unsubstituted    C₁-C₁₈alkyl; or C₁-C₁₈alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy, phenyl,    naphthyl and pyridyl; unsubstituted aryl or aryl, which is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂,    carb-C₁-C₆alkoxy, C₁-C₆alkoxy and C₁-C₄-alkyl,-   Y₃′ is hydrogen; an alkali metal ion or ammonium ion, and-   r is any number from 0 to 4, preferably any number from 1 to 4,-   r′ is any number from 1 to 4.

Other interesting phthalocyanine compounds which can be used accordingto the invention have the formula

in which

-   PC, Me, L and D are as defined in formula (4),-   R₁₂′ and R₁₃′ independently of one another are hydrogen; phenyl;    sulfophenyl; carboxyphenyl; C₁-C₆alkyl; hydroxy-C₁-C₆alkyl;    cyano-C₁-C₆alkyl; sulfo-C₁-C₆alkyl; carboxy-C₁-C₆alkyl or    halogen-C₁-C₆alkyl or R₁₂′ and R₁₃′ together with the nitrogen atom    form the morpholine ring,-   q′ is an integer from 2 to 6,-   r is a number from 1 to 4, and-   r′ is any number from 1 to 4,    where, if r is >1, the radicals

present in the molecule may be identical or different.

Further interesting phthalocyanine compounds which can be used accordingto the invention have the formula

in which

-   PC, Me, L and D are as defined in formula (4),-   Y′₃ is hydrogen; an alkali metal ion or ammonium ion,-   q′ is an integer from 2 to 6,-   R₁₂′ and R₁₃′ independently of one another are hydrogen; phenyl;    sulfophenyl; carboxyphenyl; C₁-C₆alkyl; hydroxy-C₁-C₆alkyl;    cyano-C₁-C₆alkyl; sulfo-C₁-C₆alkyl; carboxy-C₁-C₆alkyl or    halogen-C₁-C₆alkyl or R₁₂′ and R₁₃′ together with the nitrogen atom    form the morpholine ring,-   m′ is 0 or 1; and-   r′ is any number from 1 to 4-   r and r₁ independently of one another are any number from 0.5 to 2,    the sum r+r₁ being at least 1, but no more than 3.

If the central atom Me in the phthalocyanine ring is Si(IV), thephthalocyanines used according to the invention may also have axialsubstituents (=R₂₁) in addition to the substituents on the phenyl ringof the phthalocyanine ring. Such phthalocyanines have, for example, theformula

in which

-   R₂₁ is hydroxyl; C₁-C₂₂alkyl; branched C₃-C₂₂alkyl; C₁-C₂₂alkenyl;    branched C₃-C₂alkenyl and mixtures thereof; C₁-C₂alkoxy; a sulfo or    carboxyl radical; a radical of the formula

-    a branched alkoxy radical of the formula

-    alkylethyleneoxy unit of the formula    -(T₁)_(d)-(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of the formula    COOR₁₈, and-   U is [Q₁]⁺A_(s) ⁻ or Q₂, wherein-   R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, B₂, B₃, M, Q₁, Q₂, A⁻, T₁,    X₁, X₄, Y₂, Z₂ ⁻, a, b, c, d, e, r, r′, s, v and w are as defined    above (including the preferences).

Especially preferred compounds of formula (1a) and (1b) have formula

wherein

-   Me is Zn, AlZ₁, Si(IV)-(Z₁)₂ or Ti(IV)-(Z₁)₂, wherein Z₁ is    chloride, fluorine, bromine or hydroxyl,-   each Q₁ is independently of each other a sulfo or carboxyl group; or    a radical of the formula —SO₂X₂—R₁—X₃ ⁺; —O—R₁—X₃ ⁺ or —(CH₂)_(t)—Y₁    ⁺,    -   in which    -   R₁ is a branched or unbranched C₁-C₄alkylene; 1,3-phenylene or        1,4-phenylene,    -   X₂ is —NH— or —N(C₁-C₄alkyl)-,    -   X₃ ⁺ is a group of the formula

-   -   or, in the case where R₁=C₁-C₄alkylene, also a group of the        formula

-   -   Y₁ ⁺ is a group of the formula

-   -   t is 0 or 1,    -   wherein the above formulae    -   R₂ and R₃ independently of one another are C₁-C₆alkyl,    -   R₄ is C₁-C₄alkyl; pentyl; hexyl or NR₇R₈,    -   R₅ and R₆ independently of one another are C₁-C₄alkyl,    -   R₇ and R₈ independently of one another are hydrogen or        C₁-C₄alkyl,    -   R₉ and R₁₀ independently of one another are unsubstituted        C₁-C₄alkyl or C₁-C₄alkyl substituted by at least one substituent        chosen from the group consisting of hydroxyl, cyano, carboxyl,        SO₃H, —NH₂, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and        pyridyl,    -   u is from 1 to 6,    -   A₁ is a unit which completes an pyrrole-; imidazol-; pyridine-;        pyrazine-; pyrimidine-; pyridazine-ring, and    -   B₁ is a unit which completes a morpholino-; pyrrolidine-;        piperazine- or piperidine-ring,

-   each Q₂ is independently from each other hydroxyl; C₁-C₁₀alkyl;    branched C₃-C₁₀alkyl; C₂-C₁₀alkenyl; branched C₃-C₁₀alkenyl and    mixtures thereof; C₁-C₁₀alkoxy; a sulfo or carboxyl radical; a    radical of the formula

-    a branched alkoxy radical of the formula

an alkylethyleneoxy unit of the formula-(T₁)_(d)-(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of the formula COOR₁₈,

-   -   in which    -   B₂ is hydrogen; hydroxyl; C₁-C₁₈alkyl; C₁-C₁₈alkoxy; —CO₂H;        —CH₂COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁; —PO₃ ²⁻M₁; —OPO₃ ²⁻M₁; and        mixtures thereof,    -   B₃ is hydrogen; hydroxyl; —COOH; —SO₃ ^(−M) ₁; —OSO₃ ⁻M₁ or        C₁-C₄alkoxy,    -   M₁ is hydrogen; alkalimetal-ion or an ammonium ion,    -   T₁ is —O— or —NH—,    -   X₁ and X₄ independently of one another are —O—; —NH— or        —N(C₁-C₄alkyl)-,    -   R₁₁ and R₁₂ independently of one another are hydrogen; a sulfo        group and salts thereof; a carboxyl group and salts thereof or a        hydroxyl group; at least one of the radicals R₁₁ and R₁₂ being a        sulfo or carboxyl group or salts thereof,    -   Y₂ is —O—; —S—; —NH— or —N(C₁-C₄alkyl)-,    -   R₁₃ and R₁₄ independently of one another other are hydrogen;        C₁-C₄alkyl; hydroxy-C₁-C₄alkyl; cyano-C₁-C₄alkyl;        sulfo-C₁-C₄alkyl; carboxy or halogen-C₁-C₄alkyl; unsubstituted        phenyl or phenyl substituted by at least one substitutent chosen        from the group consisting of halogen, C₁-C₄alkyl and        C₁-C₄alkoxy; sulfo or carboxyl or R₁₃ and R₁₄ together with the        nitrogen atom to which they are bonded form a form morpholino,        piperazine or piperidine ring,    -   R₁₅ and R₁₆ independently of one another are C₁-C₄alkyl or        aryl-C₁-C₄alkyl radicals,    -   R₁₇ is hydrogen; an unsubstituted C₁-C₄alkyl or C₁-C₄alkyl        substituted by at least one substitutent chosen from the group        consisting of halogen, hydroxyl, cyano, SO₃H, —NH₂, phenyl,        carboxyl, carb-C₁-C₄alkoxy or C₁-C₆alkoxy,    -   R₁₈ is C₁-C₁₀alkyl; branched C₃-C₁₀alkyl; C₁-C₁₀alkenyl or        branched C₃-C₁₀alkenyl; C₃-C₂₂glycol; C₁-C₁₀alkoxy; branched        C₃-C₁₀alkoxy; and mixtures thereof,    -   M is hydrogen; Na⁺; K⁺ or an ammonium ion,    -   Z₂ ⁻ a is a alkanolate; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻; BF₄ ⁻;        PF₆ ⁻; R₀SO₃ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻; citrate ion;        tartrate ion or oxalate ion, wherein R₀ is hydrogen; or        unsubstituted C₁-C₁₈alkyl; or C₁-C₁₈alkyl, which is substituted        by at least one substituent chosen from the group consisting of        hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy,        C₁-C₆alkoxy, phenyl, naphthyl and pyridyl; unsubstituted aryl or        aryl, which is substituted by at least one substituent chosen        from the group consisting of hydroxyl, cyano, carboxyl, SO₃H,        —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy and C₁-C₄-alkyl,    -   a is 0 or 1,    -   b is from 0 to 6,    -   c is from 0 to 100,    -   d is 0; or 1,    -   e is from 0 to 22,    -   v is an integer from 2 to 12,    -   w is 0 or 1, and    -   A⁻ is an organic or inorganic anion, and    -   s is equal to r₂, r₃, r₄ and r₅ in cases of monovalent anions A⁻        and is ≦r₂, r₃, r₄ and r₅ in cases of polyvalent anions, it        being necessary for A_(s) ⁻ to compensate the positive charge;        where, when r₂, r₃, r₄ and r₅≠1, the radicals Q₁ can be        identical or different,

-   each L is independently from each other a direct bond; —SO₂—; —O—;    —OR₁₉—; —OR₁₉O—; —OR₁₉N(R₂₀)—; —N(R₂₀)—; —(CH₂CH₂O—)_(n)—; —C(O)—;    —C(O)N(R₂₀)—; —N(R₂₀)C(O)—; —OC(O)—; —C(O)O—; —S—; unsubstituted,    linear or branched C₁-C₁₈alkylene; linear or branched    C₁-C₁₈alkylene, which is substituted by at least one substituent    chosen from the group consisting of hydroxyl, cyano, SO₃H, —NH₂,    carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and    pyridyl; unsubstituted C₅-C₁₈arylene; C₅-C₁₈arylene, which is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, carboxyl, carb-C₁-C₄alkoxy,    C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted, linear or branched    C₁-C₁₈alkylene-C₅-C₁₈aryl; linear or branched    C₁-C₁₈alkylene-C₅-C₁₈aryl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl,    phenyl, naphthyl and pyridyl; unsubstituted, linear or branched    C₅-C₁₈arylene-C₁-C₁₈alkyl or linear or branched    C₅-C₁₈arylene-C₁-C₁₈alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl,    phenyl, naphthyl and pyridyl, wherein    -   R₁₉ is unsubstituted, linear or branched C₁-C₁₈alkylene; linear        or branched C₁-C₁₈alkylene, which is substituted by at least one        substituent chosen from the group consisting of hydroxyl, cyano,        SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,        naphthyl and pyridyl; unsubstituted C₅-C₁₈arylene;        C₅-C₁₈arylene, which is substituted by at least one substituent        chosen from the group consisting of hydroxyl, cyano, SO₃H, —NH₂,        carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl;        unsubstituted, linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl;        linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl, which is        substituted by at least one substituent chosen from the group        consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,        carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and        pyridyl; unsubstituted, linear or branched        C₅-C₁₈arylene-C₁-C₁₈alkyl or linear or branched        C₅-C₁₈arylene-C₁-C₁₈alkyl, which is substituted by at least one        substituent chosen from the group consisting of hydroxyl, cyano,        carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,        naphthyl and pyridyl,    -   R₂₀ is unsubstituted, linear or branched C₁-C₁₈alkyl; linear or        branched C₁-C₁₈alkyl, which is substituted by at least one        substituent chosen from the group consisting of hydroxyl, cyano,        SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,        naphthyl and pyridyl; unsubstituted C₅-C₁₈aryl; C₅-C₁₈aryl,        which is substituted by at least one substituent chosen from the        group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,        carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted,        linear or branched C₁-C₁₈alkoxy or linear or branched        C₁-C₁₈alkoxy, which is substituted by at least one substituent        chosen from the group consisting of hydroxyl, cyano, SO₃H, —NH₂,        carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and        pyridyl,    -   n is 1; 2; 3 or 4,

-   each D is independently from each other a dyestuff radical of    formula (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X),    (XI), (XII), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII), (XIX),    (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV), (XXVI), (XXVIIa),    (XXVIIb), (XXVIIc), (XXVIId), (XXVIII), (XXIX), (XXX), (XXXI),    (XXXII), (XXXIII), (XXXIV), (XXXV), (I′), (II′), (III′), (IV′),    (V′), (VI′), (VIIa′), (VIIb′), (VIII′), (IX′), (X′), (XI′), (XII′),    (XIII′), (XIV′), (XV′), (XVI′), (XVII′), (XVIII′), (XIX′), (XX′),    (XXI′), (XXVIIa′), (XXVIIb′), (XXVIIc′), (XXVIId′), (XXVIII′),    (XXIX′), (XXX′), (XXXI′), (XXXII′),

-   r₂ is 0 or 1,

-   r₃ is 0 or 1, and

-   r₄ is 0 or 1.

Usually, the inventive shading process is part of a laundry washingprocess. It can be part of any step of the laundry washing process(Pre-soaking, main washing and after-treatment). The process can becarried out in a washing machine as well as by hand. The usual washingtemperature is between 5° C. and 95° C.

The washing or cleaning agents are usually formulated that the washingliquor has pH value of about 6.5-11, preferably 7.5-11 during the wholewashing procedure.

The liquor ration in the washing process is usually 1:4 to 1:40,preferably 1:4 to 1:15, more preferably 1:4 to 1:10, especiallypreferably 1:5 to 1:9.

The washing procedure is usually done in washing machine.

There are various types of washing machines, for example:

-   -   top-loader-washing machines with a vertical rotating axis; these        machines, which have usually a capacity of about 45 to 83        litres, are used for washing processes at temperatures of        10-50° C. and washing cycles of about 10-60 minutes. Such types        of washing machines are often used in the USA;    -   front-loader-washing machine with a horizontal rotating axis;        these machines, which have usually a capacity of about 8 to 15        litres, are used for washing processes at temperatures of        30-95° C. and washing cycles of about 10-60 minutes. Such types        of washing machines are often used in Europe;    -   top-loader-washing machines with a vertical rotating axis; these        machines, which have usually a capacity of about 26 to 52        litres, are used for washing processes at temperatures of        5-25° C. and washing cycles of about 8-15 minutes. Such types of        washing machines are often used in Japan.

The washing, cleaning, disinfecting or bleaching agent according to theinvention can also be used in a soaking process, where the stainedtextiles are left for 0.5-24 hours in a solution or suspension of thedetergent and/or bleaching laundry additive without agitation. Soakingcan take place for example in a bucket or in a washing machine. Usuallythe textiles are washed and/or rinsed after the soaking process.

A further embodiment of the present invention relates to a shadingcomposition (A) comprising at least one compound of formula (1a) and/or(1b), as defined above.

A preferred embodiment of the present invention relates to a shadingcomposition (A′) comprising at least one compound of formula (2a), (3),(4), (4a), (5), (6) and/or (7), as defined above.

A more preferred embodiment of the present invention relates to ashading composition (A″) comprising at least one compound of formula (8)and/or (9), as defined above.

The shading compositions (A), (A′) and (A″) may be in any physical form,preferably in a solid or liquid form.

Granulates are preferred as solid formulation.

The present invention also relates to granulates (G) comprising

-   -   a) from 2 to 75% by weight (wt-%) of at least one shading        composition (A), (A′) and/or (A″), based on the total weight of        the granulate,    -   b) from 10 to 95 wt-% of at least one further additive, based on        the total weight of the granulate, and    -   c) from 0 to 15 wt-% water, based on the total weight of the        granulate.

The sum of the wt-% of components a)-c) is always 100%.

The granulates according to the invention can be encapsulated or not.

Encapsulating materials include especially water-soluble andwater-dispersible polymers and waxes. Of those materials, preference isgiven to polyethylene glycols, polyamides, polyacrylamides, polyvinylalcohols, polyvinylpyrrolidones, gelatin, hydrolyzed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, and alsopolyacrylates, paraffins, fatty acids, copolymers of ethyl acrylate withmethacrylate and methacrylic acid, and poly-methacrylates.

The granulates according to the invention contain from 2 to 75 wt-%,preferably from 2 to 60 wt-%, especially from 5 to 55 wt-%, of componenta), based on the total weight of the granulate.

The granulates in the formulations according to the invention containfrom 10 to 95 wt-%, preferably from 10 to 85 wt-%, especially from 10 to80 wt-%, of at least one further additive (component b)), based on thetotal weight of the granulate.

Such further additives may be anionic or non-ionic dispersing agents;water-soluble organic polymers; inorganic salts; low-molecular-weightorganic acids or a salts thereof; wetting agents; disintegrants such as,for example, powdered or fibrous cellulose, microcrystalline cellulose;fillers such as, for example, dextrin; water-insoluble or water-solubledyes or pigments; and also dissolution accelerators and opticalbrighteners. Aluminium silicates such as zeolites, and also compoundssuch as talc, kaolin, TiO₂, SiO₂ or magnesium trisilicate may also beused in small amounts.

The anionic dispersing agents used are, for example, the commerciallyavailable water-soluble anionic dispersing agents for dyes, pigmentsetc.

The following products, especially, come into consideration:condensation products of aromatic sulfonic acids and formaldehyde,condensation products of aromatic sulfonic acids with unsubstituted orchlorinated biphenyls or biphenyl oxides and optionally formaldehyde,(mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerizedorganic sulfonic acids, sodium salts of polymerizedalkylnaphthalenesulfonic acids, sodium salts of polymerizedalkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates,methylene-linked condensation products of arylsulfonic acids andhydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acids,sodium salts of alkyl diglycol ether sulfates, sodium salts ofpolynaphthalene-methanesulfonates, ligno- or oxyligno-sulfonates orheterocyclic polysulfonic acids. Especially suitable anionic dispersingagents are condensation products of naphthalene-sulfonic acids withformaldehyde, sodium salts of polymerized organic sulfonic acids,(mono-/di-)alkylnaphthalenesulfonates, polyalkylated polynucleararylsulfonates, sodium salts of polymerized alkylbenzenesulfonic acid,lignosulfonates, oxylignosulfonates and condensation products ofnaphthalenesulfonic acid with a polychloromethylbiphenyl.

Suitable non-ionic dispersants are especially compounds having a meltingpoint of, preferably, at least 35° C. that are emulsifiable, dispersibleor soluble, for example the following compounds:

-   1. fatty alcohols having from 8 to 22 carbon atoms, especially cetyl    alcohol;-   2. addition products of, preferably, from 2 to 80 mol of alkylene    oxide, especially ethylene oxide, wherein some of the ethylene oxide    units may have been replaced by substituted epoxides, such as    styrene oxide and/or propylene oxide, with higher unsaturated or    saturated monoalcohols, fatty acids, fatty amines or fatty amides    having from 8 to 22 carbon atoms or with benzyl alcohols, phenyl    phenols, benzyl phenols or alkyl phenols, the alkyl radicals of    which have at least 4 carbon atoms;-   3. alkylene oxide, especially propylene oxide, condensation products    (block polymers);-   4. ethylene oxide/propylene oxide adducts with diamines, especially    ethylenediamine;-   5. reaction products of a fatty acid having from 8 to 22 carbon    atoms and a primary or secondary amine having at least one    hydroxy-lower alkyl or lower alkoxy-lower alkyl group, or alkylene    oxide addition products of such hydroxyalkyl-group-containing    reaction products;-   6. sorbitan esters, preferably with long-chain ester groups, or    ethoxylated sorbitan esters, such as polyoxyethylene sorbitan    monolaurate having from 4 to 10 ethylene oxide units or    polyoxyethylene sorbitan trioleate having from 4 to 20 ethylene    oxide units;-   7. addition products of propylene oxide with a tri- to hexa-hydric    aliphatic alcohol having from 3 to 6 carbon atoms, e.g. glycerol or    pentaerythritol; and-   8. fatty alcohol polyglycol mixed ethers, especially addition    products of from 3 to 30 mol of ethylene oxide and from 3 to 30 mol    of propylene oxide with aliphatic monoalcohols having from 8 to 22    carbon atoms.

Especially suitable non-ionic dispersants are surfactants of formula

R₂₂—O-(alkylene-O)_(n)—R₂₃  (10),

wherein

-   R₂₃ is C₈-C₂₂alkyl or C₈-C₁₈alkenyl,-   R₂₃ is hydrogen; C₁-C₄alkyl; a cycloaliphatic radical having at    least 6 carbon atoms or benzyl,-   “alkylene” is an alkylene radical having from 2 to 4 carbon atoms    and-   n is a number from 1 to 60.

The substituents R₂₂ and R₂₃ in formula (10) are advantageously each thehydrocarbon radical of an unsaturated or, preferably, saturatedaliphatic monoalcohol having from 8 to 22 carbon atoms. The hydrocarbonradical may be straight-chain or branched. R₂ and R₂₃ are preferablyeach independently of the other an alkyl radical having from 9 to 14carbon atoms.

Aliphatic saturated monoalcohols that come into consideration includenatural alcohols, e.g. lauryl alcohol, myristyl alcohol, cetyl alcoholor stearyl alcohol, and also synthetic alcohols, e.g. 2-ethylhexanol,1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol,trimethylhexanol, trimethylnonyl alcohol, decanol, C₉-C₁₁oxo-alcohol,tridecyl alcohol, isotridecyl alcohol and linear primary alcohols(Alfols) having from 8 to 22 carbon atoms. Some examples of such Alfolsare Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) and Alfol(16-18). (“Alfol” is a registered trade mark).

Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol,hexadecenyl alcohol and oleyl alcohol.

The alcohol radicals may be present singly or in the form of mixtures oftwo or more components, e.g. mixtures of alkyl and/or alkenyl groupsthat are derived from soybean fatty acids, palm kernel fatty acids ortallow oils.

(Alkylene-O) chains are preferably divalent radicals of the formulae

Examples of a cycloaliphatic radical are cycloheptyl, cyclooctyl andpreferably cyclohexyl. As non-ionic dispersants there come intoconsideration preferably surfactants of formula

wherein

-   R₂₄ is C₈-C₂alkyl,-   R₂₅ is hydrogen or C₁-C₄alkyl,-   Y₁, Y₂, Y₃ and Y₄ are each independently of the others hydrogen;    methyl or ethyl,-   n₂ is a number from 0 to 8, and-   n₃ is a number from 2 to 40.

Further important non-ionic dispersants correspond to formula

wherein

-   R₂₆ is C₉-C₁₄alkyl,-   R₂₇ is C₁-C₄alkyl,-   Y₅, Y₆, Y₇ and Y₈ are each independently of the others hydrogen;    methyl or ethyl, one of the radicals Y₅, Y₆ and one of the radicals    Y₇, Y₈ always being hydrogen, and-   n₄ and n₅ are each independently of the other an integer from 4 to    8.

The non-ionic dispersants of formulae (10) to (12) can also be used inthe form of mixtures. For example, as surfactant mixtures there comeinto consideration non-end-group-terminated fatty alcohol ethoxylates offormula (10), e.g. compounds of formula (10) wherein

-   R₂₂ is C₈-C₂₂alkyl,-   R₂₃ is hydrogen and-   the alkylene-O chain is the radical —(CH₂—CH₂—O)— and    also end-group-terminated fatty alcohol ethoxylates of formula (12).

Examples of non-ionic dispersants of formulae (10), (11) and (12)include reaction products of a C₁₀-C₁₃fatty alcohol, e.g. aC₁₃oxo-alcohol, with from 3 to 10 mol of ethylene oxide, propylene oxideand/or butylene oxide or the reaction product of one mol of a C₁₃fattyalcohol with 6 mol of ethylene oxide and 1 mol of butylene oxide, itbeing possible for the addition products each to be end-group-terminatedwith C₁-C₄alkyl, preferably methyl or butyl. Such dispersants can beused singly or in the form of mixtures of two or more dispersants.

Instead of or in addition to the dispersing agent or agents, thegranulates according to the invention may comprise a water-solubleorganic polymer, which may also have dispersing properties. Suchpolymers may be used singly or as mixtures of two or more polymers. Aswater-soluble polymers (which may, but need not, have film-formingproperties), there come into consideration, for example, gelatins,polyacrylates, polymethacrylates, copolymers of ethyl acrylate, methylmethacrylate and methacrylic acid (ammonium salt),polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, copolymers ofvinylpyrrolidone with long-chain olefins,poly(vinylpyrrolidone/dimethylaminoethyl methacrylates), copolymers ofvinyl pyrrolidone/dimethylaminopropyl methacrylamides, copolymers ofvinylpyrrolidone/dimethylaminopropyl acrylamides, quaternised copolymersof vinyl pyrrolidones and dimethylaminoethyl methacrylates, terpolymersof vinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates,copolymers of vinylpyrrolidone and methacrylamidopropyltrimethylammoniumchloride, terpolymers of caprolactam/vinylpyrrolidone/dimethylaminoethylmethacrylates, copolymers of styrene and acrylic acid, polycarboxylicacids, polyacrylamides, carboxymethyl cellulose, hydroxymethylcellulose, polyvinyl alcohols, hydrolyzed and non-hydrolyzed polyvinylacetate, copolymers of maleic acid with unsaturated hydrocarbons andalso mixed polymerization products of the mentioned polymers. Furthersuitable substances are polyethylene glycol (MW=2000-20 000), copolymersof ethylene oxide with propylene oxide (MW>3500), condensation products(block polymerization products) of alkylene oxide, especially propyleneoxide, copolymers of vinylpyrrolidone with vinyl acetate, ethyleneoxide-propylene oxide addition products with diamines, especiallyethylenediamine, polystyrenesulfonic acid, polyethylene-sulfonic acid,copolymers of acrylic acid with sulfonated styrenes, gum arabic,hydroxypropyl methylcellulose, sodium carboxymethyl cellulose,hydroxypropyl methylcellulose phthalate, maltodextrin, starch, sucrose,lactose, enzymatically modified and subsequently hydrated sugars, as areobtainable under the name “Isomalt”, cane sugar, polyaspartic acid andtragacanth.

Among those water-soluble organic polymers, special preference is givento carboxymethyl cellulose, polyacrylamides, polyvinyl alcohols,polyvinylpyrrolidones, gelatins, hydrolyzed polyvinyl acetates,copolymers of vinylpyrrolidone and vinyl acetate, maltodextrins,polyaspartic acid and also polyacrylates and polymethacrylates.

For use as inorganic salts there come into consideration carbonates,hydrogen carbonates, phosphates, polyphosphates, sulfates, silicates,sulfites, borates, halides and pyrophosphates, preferably in the form ofalkali metal salts. Preference is given to water-soluble salts such as,for example, alkali metal chlorides, alkali phosphates, alkalicarbonates, alkali polyphosphates and alkali sulfates and water-solublesalts used in washing agent and/or washing agent additive formulations.

There come into consideration as low-molecular-weight acids, forexample, mono- or poly-carboxylic acids. Of special interest arealiphatic carboxylic acids, especially those having a total number offrom 1 to 12 carbon atoms. Preferred acids are aliphatic C₁-C₁₂-mono- or-poly-carboxylic acids, the monocarboxylic acids being especially thosehaving at least 3 carbon atoms in total. As substituents of thecarboxylic acids there come into consideration, for example, hydroxy andamino, especially hydroxy. Special preference is given to aliphaticC₂-C₁₂polycarboxylic acids, especially aliphatic C₂-C₆polycarboxylicacids. Very special preference is given to hydroxy-substituted aliphaticC₂-C₆polycarboxylic acids. These compounds may be used in the form ofthe free acid or a salt, especially an alkali salt.

There may also be used aminopolycarboxylates (e.g. sodiumethylenediaminetetraacetate), phytates, phosphonates,aminopolyphosphonates (e.g. sodium ethylenediaminetetraphosphonate),aminoalkylenepoly(alkylenephosphonates), polyphosphonates,polycarboxylates or water-soluble polysiloxanes.

As examples of low-molecular-weight organic acids and salts thereofthere may be mentioned oxalic acid, tartaric acid, acetic acid,propionic acid, succinic acid, maleic acid, citric acid, formic acid,gluconic acid, p-toluenesulfonic acid, terephthalic acid, benzoic acid,phthalic acid, acrylic acid and polyacrylic acid.

The optical brighteners may be selected from a wide range of chemicaltypes such as 4,4′-bis-(triazinylamino)-stilbene-2,2′-disulfonic acids,4,4′-bis-(triazol-2-yl)stilbene-2,2′-disulfonic acids,4,4′-(diphenyl)-stilbenes, 4,4′-distyryl-biphenyls,4-phenyl-4′-benzoxazolyl-stilbenes, stilbenzyl-naphthotriazoles,4-styryl-stilbenes, bis-(benzoxazol-2-yl) derivatives,bis-(benzimidazol-2-yl) derivatives, coumarines, pyrazolines,naphthalimides, triazinyl-pyrenes, 2-styryl-benzoxazole- or-naphthoxazole derivatives, benzimidazole-benzofuran derivatives oroxanilide derivatives.

With particular reference to the use of a composition, which is anaqueous textile finishing composition, preferred4,4′-bis-(triazinylamino)-stilbene-2,2′-disulfonic acids are thosehaving the formula (13):

in whichR₂₈ and R₂₉, independently of one another, are phenyl; mono- ordisulfonated phenyl; phenylamino; mono- or disulfonated phenylamino;morpholino; —N(CH₂CH₂OH)₂; —N(CH₃)(CH₂CH₂OH); —NH₂; —N(C₁-C₄alkyl)₂;—OCH₃; —Cl; —NH—CH₂CH₂SO₃H or —NH—CH₂CH₂OH, andM is H; Na; K; Ca; Mg; ammonium; mono-, di-, tri- ortetra-C₁-C₄-alkylammonium; mono-, di- or tri-C₁-C₄-hydroxyalkylammoniumor ammonium that is di- or tri-substituted with by a mixture ofC₁-C₄-alkyl and C₁-C₄-hydroxyalkyl groups.

Especially preferred compounds of formula (13) are those in which eachR₂₈ is 2,5-disulfophenyl and each R₂₉ is morpholino; or each R₂₈ is2,5-disulfophenyl and each R₂₉ is N(C₂H₅)₂; or each R₂₈ is 3-sulfophenyland each R₂₉ is NH(CH₂CH₂OH) or N(CH₂CH₂OH)₂; or each R₂₈ is4-sulfophenyl and each R₂₉ is N(CH₂CH₂OH)₂; and, in each case, the sulfogroup is SO₃M in which M is sodium.

Preferred 4,4′-bis-(triazol-2-yl)stilbene-2,2′-disulfonic acids arethose having the formula (14):

in whichR₃₀ and R₃₁, independently of one another, are H; C₁-C₄-alkyl; phenyl ormonosulfonated phenyl, andM is H; Na; K; Ca; Mg; ammonium; mono-, di-, tri- ortetra-C₁-C₄-alkylammonium; mono-, di- or tri-C₁-C₄-hydroxyalkylammoniumor ammonium that is di- or tri-substituted with by a mixture ofC₁-C₄-alkyl and C₁-C₄-hydroxyalkyl groups.

Especially preferred compounds of formula (14) are those in which R₃₀ isphenyl, R₃₁ is H and M is sodium.

One preferred 4,4′-(diphenyl)-stilbene is that having the formula (15):

Preferably, 4,4′-distyryl-biphenyls used are those of formula (16):

in whichR₃₂ and R₃₃, independently of one another, are H; —SO₃M;—SO₂N(C₁-C₄-alkyl)₂;O—(C₁-C₄-alkyl); CN; Cl; COO(C₁-C₄-alkyl); CON(C₁-C₄-alkyl)₂ orO(CH₂)₃N⁽⁺⁾(CH₃)₂An⁽⁻⁾ in which An⁽⁻⁾ is an anion of an organic orinorganic acid, in particular a formate, acetate, propionate, glycolate,lactate, acrylate, methanephosphonate, phosphite, sulfonate, dimethyl ordiethyl phosphite anion or a mixture thereof,n is 0 or 1 andM is H; Na; K; Ca; Mg; ammonium; mono-, di-, tri- ortetra-C₁-C₄-alkylammonium; mono-, di- or tri-C₁-C₄-hydroxyalkylammoniumor ammonium that is di- or tri-substituted with by a mixture ofC₁-C₄-alkyl and C₁-C₄-hydroxyalkyl groups.

Especially preferred compounds of formula (16) are those in which n is 1and each R₃₂ is a 2-SO₃M group in which M is sodium and each R₃₃ is H,or each R₃₃ is —O(CH₂)₃N⁽⁺⁾(CH₃)₂An⁽⁻⁾ in which An⁽⁻⁾ is acetate.

Preferred 4-phenyl-4′-benzoxazolyl-stilbenes have the formula (17):

in whichR₃₄ and R₃₅, independently of one another, are H; Cl; C₁-C₄-alkyl or—SO₂—C₁-C₄-alkyl.

An especially preferred compound of formula (17) is that in which R₃₄ is4-CH₃ and R₃₅ is 2-CH₃.

Preferably, stilbenzyl-naphthotriazoles used are those of formula (18):

in which

R₃₆ is H or C₁,

R₃₇ is —SO₃M; —SO₂N(C₁-C₄-alkyl)₂; —SO₂O-phenyl or —CN,

R₃₈ is H or —SO₃M, and

M is H; Na; K; Ca; Mg; ammonium; mono-, di-, tri- ortetra-C₁-C₄-alkylammonium; mono-, di- or tri-C₁-C₄-hydroxyalkylammoniumor ammonium that is di- or tri-substituted with by a mixture ofC₁-C₄-alkyl and C₁-C₄-hydroxyalkyl groups.

Especially preferred compounds of formula (18) are those in which R₃₆and R₃₇ are H and R₃₈ is 2-SO₃M in which M is Na.

Preferably, 4-styryl-stilbenes used are those of formula:

in whichR₃₉ and R₄₀, independently of one another, are H; —SO₃M;—SO₂N(C₁-C₄-alkyl)₂; —O—(C₁-C₄-alkyl); —CN; —Cl; —COO(C₁-C₄-alkyl);—CON(C₁-C₄-alkyl)₂ or —O(CH₂)₃N⁽⁺⁾(CH₃)₂An⁽⁻⁾ in which An⁽⁻⁾ is an anionof an organic or inorganic acid, in particular a formate, acetate,propionate, glycolate, lactate, acrylate, methanephosphonate, phosphite,sulfonate, dimethyl or diethyl phosphite anion or a mixture thereof.

Especially preferred compounds of formula (19) are those in which eachof R₃₉ and R₄₀ is 2-cyano; 2-SO₃M in which M is sodium orO(CH₂)₃N⁽⁺⁾(CH₃)₂An⁽⁻⁾ in which An⁽⁻⁾ is acetate.

Preferred bis-(benzoxazol-2-yl) derivatives are those of formula (20):

in whicheach R₄₁, independently of one another, is H; C(CH₃)₃; C(CH₃)₂-phenyl;C₁-C₄-alkyl or COO—C₁-C₄-alkyl, andX is —CH═CH— or a group of formula:

Especially preferred compounds of formula (20) are those in which eachR₄₁ is H and X is

or one group R₄₁ in each ring is 2-methyl and the other R₄₁ is H and Xis —CH═CH—; or one group R₄₁ in each ring is 2-C(CH₃)₃ and the other R₄₁is H and X is

Preferred bis-(benzimidazol-2-yl) derivatives are those of formula (21):

in whichR₄₂ and R₄₃, independently of one another, are H; C₁-C₄-alkyl orCH₂CH₂OH;

R₄₄ is H or SO₃M;

X₁ is —CH═CH— or a group of formula:

M is H; Na; K; Ca; Mg; ammonium; mono-, di-, tri- ortetra-C₁-C₄-alkylammonium; mono-, di- or tri-C₁-C₄-hydroxyalkylammoniumor ammonium that is di- or tri-substituted with by a mixture ofC₁-C₄-alkyl and C₁-C₄-hydroxyalkyl groups.

Especially preferred compounds of formula (21) are those in which R₄₂and R₄₃ are each H, R₄₄ is SO₃M in which M is sodium and X₁ is —CH═CH—.

Preferred coumarines are those of formula:

in which

R₄₅ is H; —Cl or —CH₂COOH,

R₄₆ is H; phenyl; —COO—C₁-C₄-alkyl or a group of formula:

and R₄₇ is —O—C₁-C₄-alkyl; —N(C₁-C₄-alkyl)₂; —NH—CO—C₁-C₄-alkyl or agroup of formula:

-   -   in which R₂₈, R₂₉, R₃₀ and R₃₁ have their previous significance        and    -   R₄₈ is H; C₁-C₄-alkyl or phenyl.

Especially preferred compounds of formula (22) are those having theformula (23) and (24):

Preferably, pyrazolines used are those having the formula (25):

in whichR₄₉ is H; —Cl or —N(C₁-C₄-alkyl)₂,R₅₀ is H; —Cl; —SO₃M; —SO₂NH₂; —SO₂NH—(C₁-C₄-alkyl); —COO—C₁-C₄-alkyl;—SO₂—C₁-C₄-alkyl; —SO₂NHCH₂CH₂CH₂N⁽⁺⁾(CH₃)₃ orSO₂CH₂CH₂N⁽⁺⁾H(C₁-C₄-alkyl)₂An⁽⁻⁾,R₅₁ and R₅₂ are the same or different and each is H; C₁-C₄-alkyl orphenyl,

R₅₃ is H or —Cl,

An⁽⁻⁾ is an anion of an organic or inorganic acid, in particular aformate, acetate, propionate, glycolate, lactate, acrylate,methanephosphonate, phosphite, sulfonate, dimethyl or diethyl phosphiteanion or a mixture thereof andM is H; Na; K; Ca; Mg; ammonium; mono-, di-, tri- ortetra-C₁-C₄-alkylammonium; mono-, di- or tri-C₁-C₄-hydroxyalkylammoniumor ammonium that is di- or tri-substituted with by a mixture ofC₁-C₄-alkyl and C₁-C₄-hydroxyalkyl groups.

Especially preferred compounds of formula (25) are those in which R₄₉ is—Cl; R₅₀ is —SO₂CH₂CH₂N⁽⁺⁾H(C₁-C₄-alkyl)₂An⁽⁻⁾ in which An⁽⁻⁾ isphosphite and R₅₁, R₅₂ and R₅₃ are each H; or those having the formula(26) and (27):

Preferred naphthalimides are those of formula (28):

in whichR₅₄ is C₁-C₄-alkyl or —CH₂CH₂CH₂N⁽⁺⁾(CH₃)₃,R₅₅ and R₅₆, independently of one another, are —O—C₁-C₄-alkyl; —SO₃M or—NH—CO—C₁-C₄-alkyl, andM is H; Na; K; Ca; Mg; ammonium; mono-, di-, tri- ortetra-C₁-C₄-alkylammonium; mono-, di- or tri-C₁-C₄-hydroxyalkylammoniumor ammonium that is di- or tri-substituted with by a mixture ofC₁-C₄-alkyl and C₁-C₄-hydroxyalkyl groups.

Especially preferred compounds of formula (28) are those having theformula (29) and (30):

Preferred triazinyl-pyrenes used are those of formula (31):

in whicheach R₅₇, independently of one another, is C₁-C₄-alkoxy.

Especially preferred compounds of formula (31) are those in which eachR₅₇ is methoxy.

Preferred 2-styryl-benzoxazole- or -naphthoxazole derivatives are thosehaving the formula (32):

in whichR₅₈ is —CN; —Cl; —COO—C₁-C₄-alkyl or phenyl,R₅₉ and R₆₀ are the atoms required to form a fused benzene ring orR₆₀ and R₆₂, independently of one another, are H or C₁-C₄-alkyl, andR₆₁ is H; C₁-C₄-alkyl or phenyl.

Especially preferred compounds of formula (32) are those in which R₅₈ isa 4-phenyl group and each of R₅₉ to R₆₁ is H.

Preferred benzimidazole-benzofuran derivatives are those having theformula (33):

in whichR₆₃ is C₁-C₄-alkoxy,R₆₄ and R₆₅, independently of one another, are C₁-C₄-alkyl, andAn⁽⁻⁾ is an anion of an organic or inorganic acid, in particular aformate, acetate, propionate, glycolate, lactate, acrylate,methanephosphonate, phosphite, sulfonate, dimethyl or diethyl phosphiteanion or a mixture thereof.

A particularly preferred compound of formula (33) is that in which R₆₃is methoxy, R₆₄ and R₆₅ are each methyl and An⁽⁻⁾ is methane sulfonate.

Preferred oxanilide derivatives include those having the formula (34):

in whichR₆₆ is C₁-C₄alkoxy,R₆₈ is C₁-C₄alkyl; C₁-C₄alkyl-SO₃M or C₁-C₄alkoxy-SO₃M in which

-   -   M is H; Na; K; Ca; Mg; ammonium; mono-, di-, tri- or        tetra-C₁-C₄-alkylammonium; mono-, di- or        tri-C₁-C₄-hydroxyalkylammonium or ammonium that is di- or        tri-substituted with by a mixture of C₁-C₄-alkyl and        C₁-C₄-hydroxyalkyl groups and        R₆₇ and R₆₉ are the same and each is hydrogen; tert.-butyl or        SO₃M in which M has its previous significance.

Preferred FWA are those having one of the formulae:

in whichR₇₀ and R₇₁, independently of one another, are —OH; —NH₂;—O—C₁-C₄-alkyl; —O-aryl; —NH—C₁-C₄-alkyl; —N(C₁-C₄-alkyl)₂;—N(C₁-C₄-alkyl)(C₁-C₄-hydroxyalkyl); —N(C₁-C₄-hydroxyalkyl)₂; —NH-aryl;morpholino; —S—C₁-C₄-alkyl(aryl) or C₁,R₇₂ and R₇₃, independently of one another, are H; C₁-C₄-alkyl; phenyl ora group of formula:

R₇₄ is H; —Cl or —SO₃M,

R₇₅ is —CN; —SO₃M; —S(C₁-C₄-alkyl)₂ or —S(aryl)₂,R₇₆ is H; —SO₃M; —O—C₁-C₄-alkyl; —CN; —Cl; —COO—C₁-C₄-alkyl; or—CON(C₁-C₄-alkyl)₂,R₇₇ is H; C₁-C₄-alkyl; —Cl or —SO₃M,R₇₈ and R₇₉, independently of one another, are H; C₁-C₄-alkyl; —SO₃M;—Cl or —O—C₁-C₄-alkyl;R₈₀ is H or C₁-C₄-alkyl,R₈₁ is H; C₁-C₄-alkyl; —CN; —Cl; —COO—C₁-C₄-alkyl; —CON(C₁-C₄-alkyl)₂;aryl or —O-aryl; andM is H; Na; K; Ca; Mg; ammonium; mono-, di-, tri- ortetra-C₁-C₄-alkylammonium; mono-, di- or tri-C₁-C₄-hydroxyalkylammoniumor ammonium that is di- or tri-substituted with by a mixture ofC₁-C₄-alkyl and C₁-C₄-hydroxyalkyl groups andn is 0 or 1.

In the compounds of formulae (35) to (42), C₁-C₄-alkyl groups are, e.g.,methyl, ethyl, n-propyl, isopropyl and n-butyl, especially methyl. Arylgroups are naphthyl or, especially, phenyl.

Specific examples of preferred compounds of formula (35) are thosehaving the formulae:

Specific preferred examples of compounds of formula (36) are those offormulae:

in which n has its previous significance.

Preferred examples of compounds of formula (38) are those having theformulae:

Preferred examples of compounds of formula (39) are those of formulae:

A preferred example of a compound of formula (42) is that having theformula (59):

The compounds of formulae (25) to (59) are known and may be obtained byknown methods.

Further preferred FWA's are those of the class of cationicbistyrylphenyl fluorescent whitening agent having the formula (60):

in whichY is arylene, preferably 1,4-phenylene or 4,4′-diphenylene, eachoptionally substituted by chloro, methyl or methoxy,each q is independently from each other 1 or 2,each R₈₂ is independently from each other hydrogen; chloro; C₁-C₄-alkyl;C₁-C₄-alkoxy; cyano or C₁-C₄-alkoxycarbonyl,R₈₃ and R₈₄ are independently from each other C₁-C₄-alkyl; chloroethyl;methoxyethyl; p-ethoxyethyl; p-acetoxyethyl or p-cyanoethyl; benzyl orphenylethyl,each R₈₅ is independently from each other C₁-C₄-alkyl;C₂-C₃-hydroxyalkyl; p-hydroxy-γ-chloropropyl; p-cyanoethyl orC₁-C₄-alkoxy-carbonylethyl, andAn⁽⁻⁾ has its previous significance and is preferably the chloride;bromide; iodide; methosulfate; ethosulfate; benzenesulfonate orp-toluenesulfonate anion when R₈₅ is C₁-C₄-alkyl or An⁽⁻⁾ is preferablythe formate; acetate; propionate or benzoate anion when R₈₅ isβ-hydroxy-γ-chloropropyl; β-cyanoethyl or C₁-C₄-alkoxy-carbonylethyl.

Preferred compounds of formula (60) are those in which Y is1,4-phenylene or 4,4′-diphenylene; R₈₂ is hydrogen; methyl or cyano; R₈₃and R₈₄ are each methyl or cyano; and R₈₃ and An⁽⁻⁾ have theirpreviously indicated preferred meanings.

One particularly preferred compound of formula (60) is that having theformula (61):

The compounds of formula (60) and their production are described in U.S.Pat. No. 4,009,193.

A further preferred class of cationic bistyrylphenyl fluorescentwhitening agent is that having the formula (62):

in whicheach q is independently from each other 1 or 2,each R₈₂ is independently from each other hydrogen; chloro; C₁-C₄-alkyl;C₁-C₄-alkoxy; cyano or C₁-C₄-alkoxycarbonyl,Y₁ is C₂-C₄-alkylene or hydroxypropylene,each R₈₆ is independently from each other C₁-C₄-alkyl or, together withR₈₇ and the nitrogen to which they are each attached, R₈₆ forms apyrrolidine; piperidine; hexamethyleneimine or morpholine ring,each R₈₇ is independently from each other C₁-C₄-alkyl or, together withR₈₆ and the nitrogen to which they are each attached, R₈₇ forms apyrrolidine, piperidine, hexamethyleneimine or morpholine ring,each R₈₈ is independently from each other hydrogen; C₁-C₄-alkyl;C₃-C₄-alkenyl; C₁-C₄-alkoxycarbonylmethyl; benzyl; C₂-C₄-hydroxyalkyl;C₂-C₄-cyanoalkyl or, together with R₈₆ and R₈₇ and the nitrogen atom towhich they are each attached, R₈₈ forms a pyrrolidine, piperidine,hexamethyleneimine or morpholine ring,An⁽⁻⁾ is an anion of an organic or inorganic acid, in particular aformate, acetate, propionate, glycolate, lactate, acrylate,methanephosphonate, phosphite, sulfonate, dimethyl or diethyl phosphiteanion, or a mixture thereof, andeach p is independently from each other 0 or 1.

Preferred compounds of formula (62) are those in which q is 1; R₈₂ ishydrogen, chlorine, C₁-C₄-alkyl or C₁-C₄-alkoxy; Y₁ is (CH₂)₂; R₈₆ andR₈₇ are the same and each is methyl or ethyl; R₈₈ is methyl or ethyl; pis 1; and An⁽⁻⁾ is CH₃OSO₃ or C₂H₅OSO₃.

The compounds of formula (62) and their production are described in U.S.Pat. No. 4,339,393.

A further preferred class of cationic bistyrylphenyl fluorescentwhitening agent is that having the formula (63):

in which R₈₂, Y₁, An⁽⁻⁾, p and q have their previous significance,R₈₉ and R₉₀, independently of one another, are C₁-C₄-alkyl orC₂-C₃-alkenyl orR₈₉ and R₉₀, together with the nitrogen atom to which they are attached,form a pyrrolidine; piperidine; hexamethyleneimine or morpholine ring,each R₉₁ is independently from each other hydrogen; C₁-C₄-alkyl orC₂-C₃-alkenyl or R₈₉, R₉₀ and R₉₁, together with the nitrogen atom towhich they are attached, form a pyridine or picoline ring, andZ is sulfur; —SO₂—; —SO₂NH—; —O—C₁-C₄-alkylene-COO— or —OCO—.

Preferred compounds of formula (63) are those in which R₈₂ is hydrogen;chloro; C₁-C₄-alkyl or C₁-C₄-alkoxy; R₈₉ and R₉₀, independently of oneanother, are C₁-C₄-alkyl or, together with the nitrogen atom to whichthey are attached, form a pyrrolidine, piperidine or morpholine ring;R₉₁ is hydrogen; C₁-C₄-alkyl or C₃-C₄-alkenyl or R₈₉, R₉₀ and R₉₁,together with the nitrogen atom to which they are attached, form apyridine ring; and Z is sulfur; —SO₂— or —SO₂NH—.

The compounds of formula (63) and their production are described in U.S.Pat. No. 4,486,352.

A further preferred class of cationic bistyrylphenyl fluorescentwhitening agent is that having the formula (64):

in which R₈₂, R₈₉, R₉₀, R₉₁, Y₁, An(−), p and q have their previoussignificance.

Preferred compounds of formula (64) are those in which q is 1; R₈₂ ishydrogen; chloro; C₁-C₄-alkyl or C₁-C₄-alkoxy; R₈₉ and R₉₀,independently of one another, are C₁-C₄-alkyl or R₈₉ and R₉₀ togetherwith the nitrogen atom to which they are attached, form a pyrrolidine;piperidine or morpholine ring; R₉₁ is hydrogen; C₁-C₄-alkyl orC₃-C₄-alkenyl or R₈₉, R₉₀ and R₉₁, together with the nitrogen atom towhich they are attached, form a pyridine ring.

The compounds of formula (64) and their production are described in U.S.Pat. No. 4,602,087.

One preferred class of amphoteric styrene fluorescent whitening agent isthat having the formula (65):

in which R₈₂, R₈₉, R₉₀, Y₁ and q have their previous significance andZ₁ is oxygen; sulfur; a direct bond; —COO—; —CON(R₉₂)— or —SO₂N(R₉₂)— inwhich

-   -   R₉₂ is hydrogen; C₁-C₄-alkyl or cyanoethyl; and Q is —COO— or        —SO₃.

Preferred compounds of formula (65) are those in which Z₁ is oxygen; adirect bond; —CONH—; —SO₂NH— or —COO—; especially oxygen; q is 1; R₈₂ ishydrogen; C₁-C₄-alkyl; methoxy or chlorine; and R₈₉, R₉₀, Y₁ and Q havetheir previous significance.

The compounds of formula (65) and their production are described in U.S.Pat. No. 4,478,598.

One preferred class of amine oxide fluorescent whitening agent is thathaving the formula:

in whichq has its previous significance,B is a brightener radical selected from a 4,4′-distyrylbiphenyl;4,4′-divinyl-stilbene, and a 1,4′-distyrylbenzene, each optionallysubstituted by one to four substituents selected from halogen,C₁-C₄-alkyl, C₁-C₄-hydroxyalkyl, C₁-C₄-halogenoalkyl, C₁-C₄-cyanoalkyl,C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl-C₁-C₄-alkyl, carboxy-C₁-C₄-alkyl,carb-C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkenyl, C₅-C₈-cycloalkyl,C₁-C₄-alkoxy, C₁-C₄-alkenoxy, C₁-C₄-alkoxycarbonyl, carbamoyl, cyano,C₁-C₄-alkyl-sulfonyl, phenylsulfonyl, C₁-C₄-alkoxysulfonyl, sulfamoyl,hydroxyl, carboxyl, sulfo and trifluoromethyl;Z₂ is a direct bond between B and Y₂; an oxygen atom; a sulfur atom;—SO₂—; —SO₂—O—; —COO—; —CON(R₉₅)— or —SO₂N(R₉₅)— in which

-   -   R₉₅ is hydrogen or C₁-C₄-alkyl optionally substituted by        halogen, cyano, hydroxyl, C₂-C₅-carbalkoxy, C₁-C₄-alkoxy,        phenyl, chlorophenyl, methylphenyl, methoxyphenyl, carbamoyl or        sulfamoyl,        Y₂ is C₂-C₄-alkylene or C₂-C₄-alkyleneoxy-C₂-C₄-alkylene, each        optionally substituted by halogen, hydroxyl, C₂-C₅-carbalkoxy,        C₁-C₄-alkoxy, phenyl, chlorophenyl, methylphenyl, methoxyphenyl,        carbamoyl or sulfamoyl, and        R₉₃ and R₉₄, independently of one another, are C₅-C₈-cycloalkyl;        C₁-C₄-alkyl or phenyl, each optionally substituted by halogen,        hydroxyl, C₂-C₅-carbalkoxy, C₁-C₄-alkoxy, phenyl, chlorophenyl,        methylphenyl, methoxyphenyl, carbamoyl or sulfamoyl; in which,        in all the carbamoyl or sulfamoyl groups, the nitrogen atom is        optionally substituted by one or two C₁-C₄-alkyl,        C₁-C₄-hydroxyalkyl, C₂-C₅-cyanoalkyl, C₁-C₄-halogenoalkyl,        benzyl or phenyl groups.

Preferred brightener radicals B are those having the formula:

in whichq has its previous significance and the rings are optionally substitutedas indicated above.

Preferably Z₂ is oxygen; —SO₂— or —SO₂N(R₉₆)— in which R₉₆ is hydrogenor C₁-C₄-alkyl optionally substituted by hydroxyl, halogen or cyano; andR₉₃ and R₉₄, independently of one another, are C₁-C₄-alkyl optionallysubstituted by halogen, cyano, hydroxyl, C₁-C₄-alkoxy, phenyl,chlorophenyl, methylphenyl, methoxyphenyl or C₂-C₅-alkoxycarbonyl. Otherpreferred compounds of formula (64) are those in which Z₂ is oxygen;sulfur; —SO₂—; —CON(R₉₆)— or —SO₂N(R₉₆)— in which R₉₆ is hydrogen orC₁-C₄-alkyl optionally substituted by hydroxyl, halogen or cyano; and Y₂is C₁-C₄-alkylene.

The compounds of formula (66) and their production are described in U.S.Pat. No. 4,539,161.

One preferred class of cationic phosphinic acid salt fluorescentwhitening agent is that having the formula (67):

in whichq and Y₂ have their previous significance,B₁ is brightener radical,Z₃ is a direct bond; —SO₂—C₂-C₄-alkyleneoxy; —SO₂—C₂-C₄-alkylene-COO—;—SO₂—; —COO—; —SO₂—C₂-C₄-alkylene-CON(R₁₀₂)— or —SO₂N(R₁₀₂)—, in which

-   -   R₁₀₂ is hydrogen or C₁-C₄-alkyl optionally substituted by        hydroxyl, halogen or cyano;        R₉₇ is C₁-C₄-alkyl or C₂-C₄-alkenyl, each optionally substituted        by halogen, cyano, hydroxy, C₁-C₄-alkoxycarbonyl or        C₁-C₄-alkylcarbonyloxy, or R₉₇ is benzyl, optionally substituted        by halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy, or R₉₇, together with        R₉₈ or Z₃, forms a pyrrolidine, piperidine or morpholine        radical,        R₉₈ is C₁-C₄-alkyl or C₂-C₄-alkenyl, each optionally substituted        by halogen, cyano, hydroxy, C₁-C₄-alkoxycarbonyl or        C₁-C₄-alkylcarbonyloxy, or R₉₈ is benzyl, optionally substituted        by halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy, or R₉₈, together with        R₉₇, forms a pyrrolidine, piperidine or morpholine radical,        R₉₉ is C₁-C₄-alkyl,        R₁₀₀ is hydrogen or C₁-C₄-alkyl, optionally substituted by        cyano, hydroxy, C₁-C₄-alkoxycarbonyl or C₁-C₄-alkylcarbonyloxy,        and        R₁₀₁ is C₁-C₄-alkyl.

Preferably, brightener radical B₁ has the formula:

or the formula:

each optionally substituted by one to four substituents selected fromhalogen, C₁-C₄-alkyl, C₁-C₄-hydroxyalkyl, C₁-C₄-halogenoalkyl,C₁-C₄-cyanoalkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl-C₁-C₄-alkyl,carboxy-C₁-C₄-alkyl, carb-C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkenyl,C₅-C₈-cycloalkyl, C₁-C₄-alkoxy, C₁-C₄-alkenoxy, C₁-C₄-alkoxycarbonyl,carbamoyl, cyano, C₁-C₄-alkyl-sulfonyl, phenylsulfonyl,C₁-C₄-alkoxysulfonyl, sulfamoyl, hydroxyl, carboxyl, sulfo andtrifluoromethyl.

The compounds of formula (67) and their production are described inGB-A-2 023 605.

Preferred bis(triazinyl)diaminostilbene anionic fluorescent whiteningagents for use in the present invention are those having the formula(68):

Preferred dibenzofuranylbiphenyl anionic fluorescent whitening agentsfor use in the present invention are those having the formula (69):

Preferred anionic bistyrylphenyl fluorescent whitening agents for use inthe present invention are those having the formula (70):

In the formulae (68) to (70),

R₁₀₃ is phenyl, optionally substituted by one or two —SO₃M groups,R₁₀₄ is —NH—C₁-C₄-alkyl; —N(C₁-C₄-alkyl)₂; —NH—C₁-C₄-alkoxy;—N(C₁-C₄-alkoxy)₂; —N(C₁-C₄-alkyl)(C₁-C₄-hydroxyalkyl) or—N(C₁-C₄-hydroxyalkyl)₂,R₁₀₅ is H; —C₁-C₄-alkyl; —CN; —Cl or —SO₃M; R₁₀₆ and R₁₀₇, independentlyof one another, are H; C₁-C₄-alkyl; —SO₃M; —CN; —Cl or —O—C₁-C₄-alkyl,provided that at least two of R₁₀₅, R₁₀₆ and R₁₀₇ are —SO₃M and thethird group has solubilising character,R₁₀₈ is H; —SO₃M; —O—C₁-C₄-alkyl; —CN; —Cl; —COO—C₁-C₄-alkyl or—CON(C₁-C₄-alkyl)₂,M is H; Na; K; Ca; Mg; ammonium; mono-, di-, tri- ortetra-C₁-C₄-alkylammonium; mono-, di- or tri-C₁-C₄-hydroxyalkylammoniumor ammonium that is di- or tri-substituted with by a mixture ofC₁-C₄-alkyl and C₁-C₄-hydroxyalkyl groups andr is 0 or 1.

The compounds of formulae (68) to (70) are known and may be obtained byknown methods.

Especially preferred are the non-ionic or the anionic FWA's.

The granulates in the formulations according to the invention maycontain from 0 to 15 wt-% water (component c), based on the total weightof the granulate.

The granulates in the formulations according to the invention preferablyhave an average particle size of <500 μm. Greater preference is given tothe particle size of the granulates being from 40 to 400 μm.

A preferred embodiment of the present invention relates to granulates(G′) comprising

-   -   a) from 2 to 75 wt-% of at least one shading composition (A),        (A′) and/or (A″), based on the total weight of the granulate,    -   b) from 10 to 95 wt-% of at least one further additive selected        from the group consisting of anionic or non-ionic dispersing        agents; water-soluble organic polymers; inorganic salt;        low-molecular-weight organic acid or a salt thereof; wetting        agents; disintegrants such as, for example, powdered or fibrous        cellulose, microcrystalline cellulose; fillers such as, for        example, dextrin; water-insoluble or water-soluble dyes or        pigments; dissolution accelerators; optical brighteners;        aluminium silicates; talc, kaolin, TiO₂, SiO₂ and magnesium        trisilicate, and    -   c) from 0 to 15 wt-% water, based on the total weight of the        granulate.

A more preferred embodiment of the present invention relates togranulates (G″) comprising

-   -   a) from 2 to 75 wt-% of at least one composition (A′) and/or        (A″), based on the total weight of the granulate,    -   b) from 10 to 95 wt-% of at least one further additive selected        from the group consisting of anionic or non-ionic dispersing        agents; water-soluble organic polymers; inorganic salt;        low-molecular-weight organic acid or a salt thereof; wetting        agents; disintegrants such as, for example, powdered or fibrous        cellulose, microcrystalline cellulose; fillers such as, for        example, dextrin; water-insoluble or water-soluble dyes or        pigments; dissolution accelerators; optical brighteners;        aluminium silicates; talc, kaolin, TiO₂, SiO₂ and magnesium        trisilicate, and    -   c) from 0 to 15 wt-% water, based on the total weight of the        granulate.

A further embodiment is a liquid formulation (LF) comprising at leastone shading composition (A), (A′) and/or (A″).

A preferred liquid formulation (LF′) comprises

-   (a) 0.01-95 wt-%, preferably 1-80 wt-%, more preferably 5-70 wt-% of    a shading composition (A), (A′) and/or (A″), based on the total    weight of the liquid formulation,-   (b) 5-99.99 wt-%, preferably 20-99 wt-%, more preferably 30-95 wt-%,    based on the total weight of the liquid formulation, of at least one    organic solvent and-   (c) 0-10 wt-%, preferably 0-5 wt-%, more preferably 0-2 wt-%, based    on the total weight of the liquid formulation, of at least one    further additive.

As organic solvents, polar solvents are preferred. Especially preferredare C₁-C₄-alcohols or water.

If appropriate, the liquid formulation according to the invention canfurther comprise optional additives; examples are preservatives ormixtures of preservatives, such as chloroacetamide, triazine derivates,benzoisothiazolines, 2-methyl-2H-isothiazol-3 on,2-octyl-2H-isothiazol-3 on, 2-brom-2-nitropropan-1,3-diol or aqueousformaldehyde solution; Mg/Al silicates or mixtures of Mg/Al silicates,such as bentonite, montmorillonite, zeolites or highly disperse silicicacids; odour improvers and perfuming agent or mixtures thereof; antifoamagents or mixtures thereof; builders or mixtures thereof; protectivecolloids or mixtures thereof; stabilizers or mixtures thereof;sequestering agents and antifreeze agents or mixtures thereof, such aspropylene glycol.

A more preferred embodiment of the present invention relates to a liquidformulation (LF″) comprising

-   (a) 0.01-95 wt-%, preferably 1-80 wt-%, more preferably 5-70 wt-% of    a shading composition (A), (A′) and/or (A″), based on the total    weight of the liquid formulation,-   (b) 5-99.99 wt-%, preferably 20-99 wt-%, more preferably 30-95 wt-%,    based on the total weight of the liquid formulation, of    C₁-C₄-alcohols or water, and-   (c) 0-10 wt-%, preferably 0-5 wt-%, more preferably 0-2 wt-%, based    on the total weight of the liquid formulation, of at least one    additive selected from the group consisting of preservatives; Mg/Al    silicates; odour improvers; perfuming agent; antifoam agents;    builders; protective colloids; stabilizers; sequestering agents and    antifreeze agents.

The composition according to the invention is used especially in awashing or softener formulation. Such a washing or softener formulationmay be in solid, liquid, gel-like or paste-like form, for example in theform of a liquid, non-aqueous washing agent composition containing notmore than 5 wt-%, preferably from 0 to 1 wt-%, water and based on asuspension of a builder substance in a non-ionic surfactant, for exampleas described in GB-A-2 158 454.

The washing formulations may also be in the form of powders or(super-)compact powders, in the form of single- or multi-layer tablets(tabs), in the form of washing agent bars, washing agent blocks, washingagent sheets, washing agent pastes or washing agent gels, or in the formof powders, pastes, gels or liquids used in capsules or in pouches(sachets).

However, the washing agent compositions are preferably in the form ofnon-aqueous formulations, powders, tabs or granules.

The present invention accordingly relates also to washing agentformulations (WAF) comprising

-   I) from 5 to 70 wt-% A) of at least one anionic surfactant and/or B)    at least one non-ionic surfactant, based on the total weight of the    washing agent formulation,-   II) from 5 to 60 wt-% C) of at least one builder substance, based on    the total weight of the washing agent formulation,-   III) from 0 to 30 wt-% D) of at least one peroxide and, optionally,    at least one activator and/or at least one catalyst, based on the    total weight of the washing agent formulation, and-   IV) from 0.001 to 1 wt-% E) of granulate (G), (G′) and (G″) as    defined above, based on the total weight of the washing agent    formulation,-   V) from 0 to 60 wt-% F) of at least one further additive, based on    the total weight of the washing agent formulation, and-   VI) from 0 to 5 wt-% G) water, based on the total weight of the    washing agent formulation.

The sum of the wt-% of components I)-VI) in a formulation is always100%.

The anionic surfactant A) can be, for example, a sulfate, sulfonate orcarboxylate surfactant or a mixture thereof. Preferred sulfates arethose having from 12 to 22 carbon atoms in the alkyl radical, optionallyin combination with alkyl ethoxysulfates in which the alkyl radical hasfrom 10 to 20 carbon atoms.

Preferred sulfonates are e.g. alkylbenzenesulfonates having from 9 to 15carbon atoms in the alkyl radical. The cation in the case of anionicsurfactants is preferably an alkali metal cation, especially sodium.

The anionic surfactant component may be, e.g., an alkylbenzenesulfonate,an alkylsulfate, an alkylethersulfate, an olefinsulfonate, analkanesulfonate, a fatty acid salt, an alkyl or alkenyl ethercarboxylate or an α-sulfofatty acid salt or an ester thereof. Preferredare alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkylgroup, alkylsulfates having 8 to 18 carbon atoms, alkylethersulfateshaving 8 to 22 carbon atoms, and fatty acid salts being derived frompalm oil or tallow and having 8 to 22 carbon atoms. The average molarnumber of ethylene oxide added in the alkylethersulfate is preferably 1to 22, preferably 1 to 10. The salts are preferably derived from analkaline metal like sodium and potassium, especially sodium. Highlypreferred carboxylates are alkali metal sarcosinates of formulaR₁₀₉—CO(R₁₁₀)CH₂COOM₁ in which R₁₀₉ is alkyl or alkenyl having 8-20carbon atoms in the alkyl or alkenyl radical, R₁₁₀ is C₁-C₄ alkyl and M₁is an alkali metal, especially sodium.

The nonionic surfactant component may be, e.g., primary and secondaryalcohol ethoxylates, especially the C₈-C₂₀ aliphatic alcoholsethoxylated with an average of from 1 to 20 moles of ethylene oxide permole of alcohol, and more especially the C₁₀-C₁₅ primary and secondaryaliphatic alcohols ethoxylated with an average of from 1 to 10 moles ofethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactantsinclude alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides(glucamide).

The total amount of anionic surfactant and nonionic surfactant ispreferably 5-50 wt-%, preferably 5-40 wt-% and more preferably 5-30wt-%. As to these surfactants it is preferred that the lower limit is 10wt-%.

The non-ionic surfactant B) can be, for example, a condensation productof from 3 to 8 mol of ethylene oxide with 1 mol of a primary alcoholhaving from 9 to 15 carbon atoms.

As builder substance C) there come into consideration, for example,alkali metal phosphates, especially tripolyphosphates, carbonates orhydrogen carbonates, especially their sodium salts, silicates,aluminosilicates, polycarboxylates, polycarboxylic acids, organicphosphonates, aminoalkylenepoly(alkylenephosphonates) or mixtures ofthose compounds.

Especially suitable silicates are sodium salts of crystalline layeredsilicates of the formula NaHSi_(t)O_(2t+1).pH₂O orNa₂Si_(t)O_(2t+1).pH₂O wherein t is a number from 1.9 to 4 and p is anumber from 0 to 20.

Among the aluminosilicates, preference is given to those commerciallyavailable under the names zeolithe A, B, X and HS, and also to mixturescomprising two or more of those components. Zeolithe A is preferred.

Among the polycarboxylates, preference is given topolyhydroxycarboxylates, especially citrates, and acrylates and alsocopolymers thereof with maleic anhydride. Preferred polycarboxylic acidsare nitrilotriacetic acid, ethylenediaminetetraacetic acid andethylenediamine disuccinate either in racemic form or in theenantiomerically pure (S,S) form.

Phosphonates or aminoalkylenepoly(alkylenephosphonates) that areespecially suitable are alkali metal salts of1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonicacid), ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminN,N,N′,N′ tetrakis methanphosphonic acid anddiethylenetriaminepentamethylenephosphonic acid, as well as the saltstherefrom. Also preferred polyphosphonates have the following formula

whereinR₁₁₁ is CH₂PO₃H₂ or a water soluble salt thereof andd is an integer of the value 0, 1, 2 or 3are preferred.

Especially preferred are the polyphosphonates wherein b is an integer ofthe value of 1.

Suitable peroxide components include, for example, the organic andinorganic peroxides (like sodium peroxides) known in the literature andavailable commercially that bleach textile materials at conventionalwashing temperatures, for example at from 5 to 95° C.

The amount of the peroxide or the peroxide-forming substance ispreferably 0.5-30% by weight, more preferably 1-20% by weight andespecially preferably 1-15% by weight.

As the peroxide component D) there come into consideration everycompound which is capable of yielding hydrogen peroxide in aqueoussolutions, for example, the organic and inorganic peroxides known in theliterature and available commercially that bleach textile materials atconventional washing temperatures, for example at from 10 to 95° C.

The organic peroxides are, for example, mono- or poly-peroxides, ureaperoxides, a combination of a C₁-C₄alkanol oxidase and C₁-C₄alkanol(Such as methanol oxidase and ethanol as described in WO95/07972),alkylhydroxy peroxides, such as cumene hydroperoxide and t-butylhydroperoxide, organic mono peracids of formula

whereinM signifies hydrogen or a cation,R₁₁₂ signifies unsubstituted C₁-C₁₈alkyl; substituted C₁-C₁₈alkyl;unsubstituted aryl; substituted aryl; —(C₁-C₆alkylene)-aryl, wherein thealkylene and/or the alkyl group may be substituted; andphthalimidoC₁-C₈alkylene, wherein the phthalimido and/or the alkylenegroup may be substituted. Preferred mono organic peroxy acids and theirsalts are those of formula

whereinM signifies hydrogen or an alkali metal, andR₁₁₂ signifies unsubstituted C₁-C₄alkyl; phenyl; —C₁-C₂alkylene-phenylor phthalimidoC₁-C₈alkylene.

Especially preferred is CH₃COOOH and its alkali salts.

Especially preferred is also ε-phthalimido peroxy hexanoic acid and itsalkali salts.

Instead of the peroxy acid it is also possible to use organic peroxyacid precursors and H₂O₂. Such precursors are the correspondingcarboxyacid or the corresponding carboxyanhydrid or the correspondingcarbonylchlorid, or amides, or esters, which can form the peroxy acidson perhydrolysis. Such reactions are commonly known.

Peroxy acids may also be generated from precursers such as bleachactivators, that is to say compounds that, under perhydrolysisconditions, yield unsubstituted or substituted perbenzo- and/orperoxo-carboxylic acids having from 1 to 10 carbon atoms, especiallyfrom 2 to 4 carbon atoms. Suitable bleach activators include thecustomary bleach activators, mentioned at the beginning, that carry O-and/or N-acyl groups having the indicated number of carbon atoms and/orunsubstituted or substituted benzoyl groups. Preference is given topolyacylated alkylenediamines, especially tetraacetylethylenediamine(TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU),N,N-diacetyl-N,N-dimethylurea (DDU), acylated triazine derivatives,especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),compounds of formula:

wherein R₁₁₃ is a sulfonate group, a carboxylic acid group or acarboxylate group, and wherein R₁₁₄ is linear or branched (C₇-C₁₅)alkyl,especially activators known under the names SNOBS, SLOBS and DOBA,acylated polyhydric alcohols, especially triacetin, ethylene glycoldiacetate and 2,5-diacetoxy-2,5-dihydrofuran, and also acetylatedsorbitol and mannitol and acylated sugar derivatives, especiallypentaacetylglucose (PAG), sucrose polyacetate (SUPA),pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well asacetylated, optionally N-alkylated glucamine and gluconolactone. It isalso possible to use the combinations of conventional bleach activatorsknown from German Patent Application DE-A-44 43 177. Nitrile compoundsthat form perimine acids with peroxides also come into consideration asbleach activators.

Also suitable are diperoxyacids, for example, 1,12-diperoxydodecanedioicacid (DPDA), 1,9-diperoxyazelaic acid, diperoxybrassilic acid;diperoxysebasic acid, diperoxyisophthalic acid,2-decyldiperoxybutane-1,4-diotic acid and 4,4′-sulphonylbisperoxybenzoicacid.

Preferably, however, inorganic peroxides are used, for examplepersulfates, perborates, percarbonates and/or persilicates.

Example of suitable inorganic peroxides are sodium tetrahydrate orsodium perborated monohydrate, inorganic peroxyacid compounds, such asfor example potassium monopersulphate (MPS). If organic or inorganicperoxyacids are used as the peroxygen compound, the amount thereof willnormally be within the range of about 2-10 wt-%, preferably from 4-8wt-%.

All these peroxy compounds may be utilized alone or in conjunction witha peroxyacid bleach precursor and/or an organic bleach catalyst notcontaining a transition metal. Generally, the bleaching composition ofthe invention can be suitably formulated to contain from 2 to 35 wt-%,preferably from 5 to 25 wt-%, of the peroxy bleaching agent.

Peroxyacid bleach precursors are known and amply described inliterature, such as in the British Patents 836988; 864,798; 907,356;1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522;EP-A-0174132; EP-A-0120591; and U.S. Pat. Nos. 1,246,339; 3,332,882;4,128,494; 4,412,934 and 4,675,393. Preferred one are those disclosed inWO 01/05925), especially preferred the 1:1 Mn(III) complexes.

Another useful class of peroxyacid bleach precursors is that of thecationic i.e. quaternary ammonium substituted peroxyacid precursors asdisclosed in U.S. Pat. Nos. 4,751,015 and 4,397,757, in EP-A0284292 andEP-A-331,229. Examples of peroxyacid bleach precursors of this classare: 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonatechloride—(SPCC), N-octyl,N,N-dimethyl-N10-carbophenoxy decyl ammoniumchloride—(ODC), 3-(N,N,N-trimethyl ammonium) propylsodium-4-sulphophenyl carboxylate and N,N,N-trimethyl ammoniumtoluoyloxy benzene sulphonate.

A further special class of bleach precursors is formed by the cationicnitriles as disclosed in EP-A-303,520, WO 96/40661 and in EuropeanPatent Specification No.'s 458,396, 790244 and 464,880. These cationicnitriles also known as nitril quats have the formula

wherein

-   R₁₁₅ is a C₁-C₂₄alkyl; a C₁-C₂₄alkenyl; an alkaryl having a    C₁-C₂₄alkyl; a substituted C₁-C₂₄alkyl; a substituted C₁-C₂₄alkenyl;    a substituted aryl,-   R₁₁₆ and R₁₁₇ are each independently a C₁-C₃alkyl; hydroxyalkyl    having 1 to 3 carbon atoms, —(C₂H₄O)_(n)H, n being 1 to 6; —CH₂—CN-   R₁₁₈ is a C₁-C₂₀alkyl; a C₁-C₂₀alkenyl; a substituted C₁-C₂₀alkyl; a    substituted C₁-C₂₀alkenyl; an alkaryl having a C₁-C₂₄alkyl and at    least one other substituent,-   R₁₁₉, R₁₂₀, R₁₂₁, R₁₂₂ and R₁₂₃ are each independently hydrogen, a    C₁-C₁₀alkyl, a C₁-C₁₀alkenyl, a substituted C₁-C₁₀alkyl, a    substituted C₁-C₁₀alkenyl, carboxyl, sulfonyl or cyano-   R₁₂₄, R₁₂₅, R₁₂₆ and R₁₂₇ are each independently a C₁ to C₆ alkyl,-   n′ is an integer from 1 to 3,-   n″ is an integer from 1 to 16, and-   X is an anion.

Other nitril quats have the following formula

wherein

-   R₁₂₈ and R₁₂₉ form, together with the nitrogen atom to which they    are bonded, a ring comprising 4 to 6 carbon atoms, this ring may    also be substituted by C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₅-alkanoyl,    phenyl, amino, ammonium, cyano, cyanamino or chloro and 1 or 2    carbon atom(s) of this ring may also be substituted by a nitrogen    atom, by a oxygen atom, by a N—R₁₃₃-group and/or by a    R₁₃₀—N—R₁₃₃-group, wherein R₁₃₃ is hydrogen, C₁-C₅-alkyl,    C₂-C₅-alkenyl, C₂-C₅-alkinyl, phenyl, C₇-C₈-aralkyl,    C₅-C₇-cycloalkyl, C₁-C₅-alkanoyl, cyanomethyl or cyano,

R₁₃₀ is C₁-C₂₄-, preferably C₁-C₄-alkyl, C₂-C₂₄— alkenyl, preferablyC₂-C₄-alkenyl, cyanomethyl or C₁-C₄-alkoxy-C₁-C₄-alkyl,

-   R₁₃₁ and R₁₃₂ are independently from each other hydrogen,    C₁-C₄-alkyl, C₁-C₄-alkenyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl oder    C₁-C₃-alkylphenyl, preferably hydrogen, methyl or phenyl, whereby    preferably the moiety R₁₃₁ signifies hydrogen, if R₁₃₂ is not    hydrogen, and-   X is an anion.

Suitable examples of nitril quats of formula (ε) are

Other nitrile quats have the formula

whereinA is a saturated ring formed by a plurality of atoms in addition to theN₁ atom, the saturated ring atoms to include at least one carbon atomand at least one heteroatom in addition to the N₁ atom, the said oneheteroatom selected from the group consisting of O, S and N atoms, thesubstituent R₁₃₃ bound to the N₁ atom of the Formula (4) structure is(a) a C₁₋₈ alkyl or alkoxylated alkyl where the alkoxy is C₂₋₄, (b) aC₄₋₂₄cycloalkyl, (c) a C₇₋₂₄alkaryl, (d) a repeating or nonrepeatingalkoxy or alkoxylated alcohol, where the alkoxy unit is C₂₋₄, or (e)—CR₁₃₆R₁₃₇—C≡N where R₁₃₆ and R₁₃₇ are each H, a C₁₋₂₄alkyl, cycloalkyl,or alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylatedalcohol where the alkoxy unit is C₂₋₄, in Formula (φ) at least one ofthe R₁₃₄ and R₁₃₅ substituents is H and the other of R₁₃₄ and R₁₃₅ is H,a C₁₋₂₄ alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeatingalkoxyl or alkoxylated alcohol where the alkoxy unit is C₂₋₄, and Y isat least one counterion.

Any one of these peroxyacid bleach precursors can be used in the presentinvention, though some may be more preferred than others.

Of the above classes of bleach precursors, the preferred classes are theesters, including acyl phenol sulphonates and acyl alkyl phenolsulphonates; the acyl-amides; and the quaternary ammonium substitutedperoxyacid precursors including the cationic nitriles.

Examples of said preferred peroxyacid bleach precursors or activatorsare sodium-4-benzoyloxy benzene sulphonate (SBOBS); N,N,N′N′-tetraacetylethylene diamine (TAED); sodium-1-methyl-2-benzoyloxybenzene-4-sulphonate; sodium-4-methyl-3-benzoloxy benzoate; SPCC;trimethyl ammonium toluoyloxy-benzene sulphonate; sodiumnonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5-trimethylhexanoyl-oxybenzene sulphonate (STHOBS); and the substituted cationicnitriles.

The precursors may be used in an amount of up to 12%, preferably from2-10% by weight, of the composition.

It will be understood that mixtures of inorganic and/or organicperoxides can also be used. The peroxides may be in a variety ofcrystalline forms and have different water contents, and they may alsobe used together with other inorganic or organic compounds in order toimprove their storage stability.

The peroxides are added to the agent preferably by mixing thecomponents, for example using a screw metering system and/or a fluidisedbed mixer.

The agents may comprise, in addition to the combination according to theinvention, one or more optical brighteners, for example from the classbis-triazinylamino-stilbenedisulfonic acid,bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl orbis-benzofuranylbiphenyl, a bis-benzoxalyl derivative,bis-benzimidazolyl derivative or coumarin derivative or a pyrazolinederivative.

The detergents used will usually contain one or more auxiliaries such assoil suspending agents, for example sodium carboxymethylcellulose; saltsfor adjusting the pH, for example alkali or alkaline earth metalsilicates; foam regulators, for example soap; salts for adjusting thespray drying and granulating properties, for example sodium sulphate;perfumes; and also, if appropriate, antistatic and softening agents;such as smectite clays; photobleaching agents; pigments; and/or shadingagents. These constituents should, of course, be stable to any bleachingsystem employed. Such auxiliaries can be present in an amount of, forexample, 0.1 to 20 wt-%, preferably 0.5 to 10 wt-%, especially 0.5 to 5wt-%, based on the total weight of the detergent.

Furthermore, the detergent can optionally contain enzymes. Enzymes canbe added to detergents for stain removal. The enzymes usually improvethe performance on stains that are either protein- or starch-based, suchas those caused by blood, milk, grass or fruit juices. Preferred enzymesare cellulases, proteases, amylases and lipases. Preferred enzymes arecellulases and proteases, especially proteases. Cellulases are enzymeswhich act on cellulose and its derivatives and hydrolyze them intoglucose, cellobiose, cellooligosaccharide. Cellulases remove dirt andhave the effect of mitigating the roughness to the touch. Examples ofenzymes to be used include, but are by no means limited to, thefollowing:

proteases as given in U.S. Pat. No. 6,242,405, column 14, lines 21 to32;lipases as given in U.S. Pat. No. 6,242,405, column 14, lines 33 to 46and as given in WO 0060063;amylases as given in U.S. Pat. No. 6,242,405, column 14, lines 47 to 56;andcellulases as given in U.S. Pat. No. 6,242,405, column 14, lines 57 to64.

Commercially available detergent proteases, such as Alcalase®,Esperase®, Everlase®, Savinase®, Kannase® and Durazym®, are sold e.g. byNOVOZYMES A/S.

Commercially available detergent amylases, such as Termamyl®, Duramyl®,Stainzyme®, Natalase®, Ban® and Fungamyl®, are sold e.g. by NOVOZYMESA/S.

Commercially available detergent ellulases, such as Celluzyme®,Carezyme® and Endolase®, are sold e.g. by NOVOZYMES A/S.

Commercially available detergent lipases, such as Lipolase®, LipolaseUltra® and Lipoprime®, are sold e.g. by NOVOZYMES A/S.

Suitable mannanases, such as Mannanaway®, are sold by NOVOZYMES A/S.

The enzymes can optionally be present in the detergent. When used, theenzymes are usually present in an amount of 0.01-5 wt-%, preferably0.05-5 wt-% and more preferably 0.1-4 wt-%, based on the total weight ofthe detergent.

Further preferred additives to the agents according to the invention aredye fixing agents and/or polymers which, during the washing of textiles,prevent staining caused by dyes in the washing liquor that have beenreleased from the textiles under the washing conditions. Such polymersare preferably polyvinylpyrrolidones, polyvinylimidazole orpolyvinylpyridine-N-oxides which may have been modified by theincorporation of anionic or cationic substituents, especially thosehaving a molecular weight in the range of from 5000 to 60000, moreespecially from 5000 to 50000. Such polymers are usually used in anamount of from 0.01 to 5 wt-%, preferably 0.05 to 5 wt-%, especially 0.1to 2 wt-%, based on the total weight of the detergent. Preferredpolymers are those given in WO-A-02/02865 (see especially page 1, lastparagraph and page 2, first paragraph).

A preferred washing agent formulation (WAF′) according to the inventionconsists of

-   I) from 5 to 70 wt-%    -   A) of at least one anionic surfactant from the group consisting        of alkylbenzenesulfonates having from 9 to 15 carbon atoms in        the alkyl radical; alkylnaphthalenesulfonates having from 6 to        16 carbon atoms in the alkyl radical in question; and alkali        metal sarcosinates of the formula

R₁₀₉—CO—N(R₁₁₀)—CH₂COOM₁,

-   -   -   wherein R₁₀₉ is alkyl or alkenyl having from 8 to 20 carbon            atoms in the alkyl or alkenyl radical,        -   R₁₁₀ is C₁-C₄alkyl and        -   M₁ is an alkali metal and/or

    -   B) at least one non-ionic surfactant from the group consisting        of condensation products of from 3 to 8 mols of ethylene oxide        with 1 mol of primary alcohol containing from 9 to 20 carbon        atoms, based on the total weight of the washing agent        formulation

-   II) from 5 to 60 wt-% C) of a builder substance from the group    consisting of alkali metal phosphates; carbonates; hydrogen    carbonates; silicates; aluminium silicates; polycarboxylates;    polycarboxylic acids; organic phosphonates and    aminoalkylenepoly(alkylenephosphonates), based on the total weight    of the washing agent formulation

-   III) from 0 to 30 wt-% D) of a peroxide from the group consisting of    organic mono- or poly-peroxides; organic peracids and salts thereof;    persulfates; perborates; percarbonates and persilicates and    optionally a bleach activator and/or bleach catalyst, based on the    total weight of the washing agent formulation

-   IV) from 0.001 to 1 wt-% E) of at least one granulate (G), (G′)    and/or (G″), based on the total weight of the washing agent    formulation,

-   V) from 0 to 60% F) of further additives from the group consisting    of optical brighteners; suspending agents for dirt; pH regulators;    foam regulators; salts for regulating the spray-drying and    granulating properties; fragrances; antistatic agents; fabric    conditioners; enzymes; bleaching agents; pigments; toning agents;    polymers which, during the washing of textiles, prevent staining    caused by dyes in the washing liquor which have been released from    the textiles under the washing conditions; and perborate activators,    based on the total weight of the washing agent formulation, and

-   VI) from 0 to 5% G) water, based on the total weight of the washing    agent formulation.

The granulates (G), (G′) and (G″) are prepared according to knownmethods. Any known method is suitable to produce granules comprising theinventive mixture. Continuous or discontinuous methods are suitable,Continuous methods, such as spray drying or fluidised bed granulationprocesses are preferred.

Especially suitable are spray-drying processes in which the activeingredient solution is sprayed into a chamber with circulating hot air.The atomisation of the solution is carried out using single or binarynozzles or is brought about by the spinning effect of a rapidly rotatingdisc. In order to increase the particle size, the spray-drying processmay be combined with additional agglomeration of the liquid particleswith solid nuclei in a fluidised bed that forms an integral part of thechamber (so-called fluidised spray). The fine particles (<100 μm)obtained by a conventional spray-drying process may, if necessary afterbeing separated from the exhaust gas flow, be fed as nuclei, withoutbeing further treated, directly into the spray cone of the atomiser ofthe spray-dryer, for the purpose of agglomeration with the liquiddroplets of the active ingredient. During the granulation step, thewater can be rapidly removed from the solutions comprisingphthalocyanine compound, and, where appropriate, further additives, andit is expressly intended that agglomeration of the droplets forming inthe spray cone, i.e. the agglomeration of droplets with solid particles,will take place. Preference is given to the use of agglomerationprocesses to produce the granulates according to the invention becausesuch processes usually yield a higher bulk weight so that the granulateshave better compatibility with washing agent formulations.

A further embodiment of the present invention comprises using, forpreparation of the granulates, phthalocyanine solutions that have beenpurified by membrane separation procedures. Such membrane separationprocesses, such as membrane filration are well known in the prior artand are described for example in “Handbuch der industriellenFest/Flüssig-Filtration”, Weinheim: Wiley-VCH 2000 or “Encyclopedia ofAnalytical Science”, S. 3035-3050, New York: Academic Press 1995 or“Ullmann” (5.) A16, 187-258.

If necessary, the granules formed in the spray-dryer are removed in acontinuous process, for example by a sieving operation. The fines andthe oversize particles are either recycled directly to the process(without being redissolved) or are dissolved in the liquid activeingredient formulation and subsequently granulated again.

The granulates (G), (G′) and (G″) are resistant to abrasion, low indust, free-flowing and can be readily metered. They are distinguishedespecially by very rapid solubility in water. The granulates (G), (G′)and (G″) preferably have a density in the range from 500 to 900 g/l,dissolve rapidly in water and do not float on the surface of the washingagent solution. They may be added in the desired concentration of thephthalocyanine compound directly to the washing agent formulation.

The content of granulates (G), (G′) and (G″) in accordance with theinvention in the formulations according to the invention is from to0.001 to 1 wt-%, preferably from 0.001 to 0.05 wt-% and very especiallyfrom 0.005 to 0.03 wt-%.

The washing agent formulation according to the invention can be preparedin a generally known manner.

A formulation in powder form can be prepared, for example, by firstpreparing an initial powder by spray-drying an aqueous slurry comprisingall of the afore-mentioned components except for components D) and E)and then adding the dry components D) and E) and mixing all of themtogether. It is also possible to start from an aqueous slurry which,although comprising components A) and C), does not comprise component B)or comprises only a portion of component B). The slurry is spray-dried;component E) is then mixed with component B) and added; and thencomponent D) is mixed in dry. The components are preferably mixed withone another in such amounts that a solid compact washing agentcomposition in granule form is obtained, having a specific weight of atleast 500 g/l.

In another preferred embodiment, the production of the washing agentcomposition is carried out in three steps. In the first step a mixtureof anionic surfactant (and, where appropriate, a small amount ofnon-ionic surfactant) and builder substance is prepared. In the secondstep that mixture is sprayed with the major portion of the non-ionicsurfactant and then, in the third step, peroxide and, where appropriate,catalyst, and the granulate according to the invention are added. Thatmethod is usually carried out in a fluidised bed. In a further preferredembodiment, the individual steps are not carried out completelyseparately, so that there is a certain amount of overlap between them.Such a method is usually carried out in an extruder, in order to obtaingranulates in the form of “megapearls”.

As an alternative thereto, the granulates according to the inventioncan, for the purpose of admixture with a washing agent in a post-dosingstep, be mixed with other washing agent components such as phosphates,zeolites, brighteners or enzymes.

A mixture of that kind for post-dosing of the granulates isdistinguished by a homogeneous distribution of the granulates accordingto the invention in the mixture and can consist of, for example, from 5to 50% granulates and from 95 to 50% sodium tripolyphosphate. Where thedark appearance of the granulate in the washing agent composition is tobe suppressed, this can be achieved, for example, by embedding thegranules in droplets of a whitish meltable substance (“water-solublewax”) or, preferably, by encapsulating the granules in a melt consistingof, for example, a water-soluble wax, as described in EP-B-0 323 407 B1,a white solid (e.g. titanium dioxide) being added to the melt in orderto reinforce the masking effect of the capsule.

The detergent may also be formulated as an aqueous liquid comprising5-50, preferably 10-35 wt-% of water or as a non-aqueous liquiddetergent, containing not more than 5, preferably 0-1 wt-% of water.Non-aqueous liquid detergent compositions can contain other solvents ascarriers. Low molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing surfactant, but polyols such asthose containing from 2 to about 6 carbon atoms and from 2 to about 6hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and1,2-propanediol) can also be used. The compositions may contain from 5wt-% to 90 wt-%, typically 10 wt-% to 50 wt-% of such carriers. Thedetergents can also be present as the so-called “unit liquid dose” form.

A further embodiment of the present invention is a fabric softenerformulation (FSF) comprising

(a) at least one shading composition (A), (A′) and/or (A″),(b) at least one fabric softener.

Fabric softeners, especially hydrocarbon fabric softeners, suitable foruse herein are selected from the following classes of compounds:

(i) Cationic quaternary ammonium salts. The counter ion of such cationicquaternary ammonium salts may be a halide, such as chloride or bromide,methyl sulphate, or other ions well known in the literature. Preferablythe counter ion is methyl sulfate or any alkyl sulfate or any halide,methyl sulfate being most preferred for the dryer-added articles of theinvention.

Examples of cationic quaternary ammonium salts include but are notlimited to

(1) Acyclic quaternary ammonium salts having at least two C₈ to C₃₀,preferably C₁₂ to C₂₂ alkyl or alkenyl chains, such as:ditallowedimethyl ammonium methylsulfate, di(hydrogenatedtallow)dimethyl ammonium methylsulfate, di(hydrogenated tallow)dimethylammonium methylchloride, distearyldimethyl ammonium methyl-sulfate,dicocodimethyl ammonium methylsulfate and the like. It is especiallypreferred if the fabric softening compound is a water insolublequaternary ammonium material which comprises a compound having two C₁₂to C₁₈ alkyl or alkenyl groups connected to the molecule via at leastone ester link. It is more preferred if the quaternary ammonium materialhas two ester links present. An especially preferred ester-linkedquaternary ammonium material for use in the invention can be representedby the formula:

wherein each R₁₃₆ group is independently selected from C₁ to C₄ alkyl,hydroxyalkyl or C₂ to C₄ alkenyl groups; T is either —O—C(O)— or—C(O)—O—, and wherein each R₁₃₇ group is independently selected from C₈to C₂₈ alkyl or alkenyl groups; and e is an integer from 0 to 5.

A second preferred type of quaternary ammonium material can berepresented by the formula:

wherein R₁₃₆, e and R₁₃₇ are as defined above.(2) Cyclic quaternary ammonium salts of the imidazolinium type such asdi(hydrogenated tallow)dimethyl imidazolinium methylsulfate,1-ethylene-bis(2-tallow-1-methyl) imidazolinium methylsulfate and thelike;(3) Diamido quaternary ammonium salts such as: methyl-bis(hydrogenatedtallow amidoethyl)-2-hydroxethyl ammonium methyl sulfate, methylbi(tallowamidoethyl)-2-hydroxypropyl ammonium methylsulfate and thelike;(4) Biodegradable quaternary ammonium salts such asN,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium methyl sulfate andN,N-di(tallowoyl-oxy-propyl)-N,N-dimethyl ammonium methyl sulfate.Biodegradable quaternary ammonium salts are described, for example, inU.S. Pat. Nos. 4,137,180, 4,767,547 and 4,789,491 incorporated byreference herein.

Preferred biodegradable quaternary ammonium salts include thebiodegradable cationic diester compounds as described in U.S. Pat. No.4,137,180, herein incorporated by reference.

(ii) Tertiary fatty amines having at least one and preferably two C₈ toC₃₀, preferably C₁₂ to C₂₂ alkyl chains. Examples include hardenedtallow-di-methylamine and cyclic amines such as 1-(hydrogenatedtallow)amidoethyl-2-(hydrogenated tallow) imidazoline. Cyclic amines,which may be employed for the compositions herein, are described in U.S.Pat. No. 4,806,255 incorporated by reference herein.

(iii) Carboxylic acids having 8 to 30 carbons atoms and one carboxylicgroup per molecule. The alkyl portion has 8 to 30, preferably 12 to 22carbon atoms. The alkyl portion may be linear or branched, saturated orunsaturated, with linear saturated alkyl preferred. Stearic acid is apreferred fatty acid for use in the composition herein. Examples ofthese carboxylic acids are commercial grades of stearic acid andpalmitic acid, and mixtures thereof, which may contain small amounts ofother acids.

(iv) Esters of polyhydric alcohols such as sorbitan esters or glycerolstearate. Sorbitan esters are the condensation products of sorbitol oriso-sorbitol with fatty acids such as stearic acid. Preferred sorbitanesters are monoalkyl. A common example of sorbitan ester is SPAN® 60(ICI) which is a mixture of sorbitan and isosorbide stearates.

(v) Fatty alcohols, ethoxylated fatty alcohols, alkylphenols,ethoxylated alkylphenols, ethoxylated fatty amines, ethoxylatedmonoglycerides and ethoxylated diglycerides.

(vi) Mineral oils, and polyols such as polyethylene glycol.

These softeners are more definitively described in U.S. Pat. No.4,134,838 the disclosure of which is incorporated by reference herein.Preferred fabric softeners for use herein are acyclic quaternaryammonium salts. Mixtures of the above mentioned fabric softeners mayalso be used.

The fabric softener formulation according to this invention comprisesabout 0.001-5 wt-%, preferably 0.001-3 wt-%, of a shading composition(A), (A′) and/or (A″), based on the total weight of the fabric softenerformulation.

The fabric softener formulation employed in the present inventionpreferably contains about 0.1 to about 95 wt-%, based on the totalweight of the fabric softening composition, of the fabric softenerformulation. Preferred is an amount of 0.5 to 50 wt-%, especially anamount of 2 to 50 wt-% and most preferably an amount of 2 to 30 wt-%.

The fabric softening composition may also comprise additives which arecustomary for standard commercial fabric softening compositions, forexample alcohols, such as ethanol, n-propanol, i-propanol, polyhydricalcohols, for example glycerol and propylene glycol; amphoteric andnonionic surfactants, for example carboxyl derivatives of imidazole,oxyethylated fatty alcohols, hydrogenated and ethoxylated castor oil,alkyl polyglycosides, for example decyl polyglucose anddodecylpolyglucose, fatty alcohols, fatty acid esters, fatty acids,ethoxylated fatty acid glycerides or fatty acid partial glycerides; alsoinorganic or organic salts, for example water-soluble potassium, sodiumor magnesium salts, non-aqueous solvents, pH buffers, perfumes, dyes,hydrotropic agents, antifoams, anti redeposition agents, enzymes,optical brighteners, antishrink agents, stain removers, germicides,fungicides, dye fixing agents or dye transfer inhibitors (as describedin WO-A-02/02865), antioxidants, corrosion inhibitors, wrinkle recoveryor wet soiling reduction agent, such as polyorganosiloxanes. The lattertwo additives are described in WO0125385.

Such additives are preferably used in an amount of 0 to 30 wt-%, basedon the total weight of the fabric softening composition. Preferred is anamount of 0 to 20 wt-%, especially an amount of 0 to 10 wt-% and mostpreferably an amount of 0 to 5 wt-%, based on the total weight of thefabric softening composition.

The fabric softener compositions are preferably in liquid aqueous form.The fabric softener compositions preferably contain a water content of25 to 90 wt-%, based on the total weight of the composition. Morepreferably the water content is 50 to 90 wt-%, especially 60 to 90 wt-%.

A preferred embodiment of the present invention is a fabric softenerformulation (FSF′) comprising

-   (a) 0.001-5 wt-% of a shading composition (A), (A′) and/or (A″),    based on the total weight of the fabric softener formulation,-   (b) 0.1-95 wt-% of at least one fabric softener selected from the    above defined classes (i)-(vi), based on the total weight of the    fabric softener formulation,-   (c) 0-30 wt-% of at least one additive selected from the group    consisting of alcohols; amphoteric and nonionic surfactants;    inorganic or organic salts; non-aqueous solvents; pH buffers;    perfumes, dyes; hydrotropic agents; antifoams; anti redeposition    agents; enzymes; optical brighteners; antishrink agents; stain    removers; germicides; fungicides; dye fixing agents or dye transfer    inhibitors; antioxidants; corrosion inhibitors; wrinkle recovery or    wet soiling reduction agent, based on the total weight of the fabric    softener formulation, and-   (d) 25-90 wt-% of water, based on the total weight of the fabric    softener formulation.

The fabric softener compositions preferably have a pH value from 2.0 to9.0, especially 2.0 to 5.0.

The fabric softener compositions can, for example, be prepared asfollows:

Firstly, an aqueous formulation of the cationic polymer is prepared asdescribed above. The fabric softener composition according to theinvention is usually, but not exclusively, prepared by firstly stirringthe active substance, i.e. the hydrocarbon based fabric softeningcomponent, in the molten state into water, then, where required, addingfurther desired additives and, finally, adding the formulation of thecationic polymer. The fabric softener composition can, for example, alsobe prepared by mixing a preformulated fabric softener with the cationicpolymer.

These fabric softener compositions are traditionally prepared asdispersions containing for example up to 30 wt-% of active material inwater. They usually have a turbid appearance. However, alternativeformulations usually containing actives at levels of 5 to 40 wt-% alongwith solvents can be prepared as microemulsions, which have a clearappearance (as to the solvents and the formulations see for example U.S.Pat. No. 5,543,067 und WO-A-98/17757).

A further embodiment of the present invention relates to new Zn-, Ca-,Mg-, Na-, K-, Al, Si-, Ti-, Ge-, Ga-, Zr-, In- or Sn-phthalocyaninecompounds to which at least one dyestuff is attached through a covalentbonding.

The present invention also relates to the compounds of formula (1a) and(1b), as defined above.

The present invention also relates to the compounds of formula (2a),(3), (4), (4a), (5), (6) and (7), as defined above.

An especially preferred embodiment of the present invention relates tocompounds of formula (8) and (9)

wherein

-   Me is Zn, AlZ₁, Si(IV)-(Z₁)₂ or Ti(IV)-(Z₁)₂, wherein Z₁ is    chloride, fluorine, bromine or hydroxyl,-   each Q₁ is independently of each other a sulfo or carboxyl group; or    a radical of the formula —SO₂X₂—R₁—X₃ ⁺; —O—R₁—X₃ ⁺ or —(CH₂)_(t)—Y₁    ⁺,    -   in which    -   R₁ is a branched or unbranched C₁-C₄alkylene; 1,3-phenylene or        1,4-phenylene,    -   X₂ is —NH— or —N(C₁-C₄alkyl)-,    -   X₃ ⁺ is a group of the formula

-   -   or, in the case where R₁=C₁-C₄alkylene, also a group of the        formula

-   -   Y₁ ⁺ is a group of the formula

-   -   t is 0 or 1,    -   wherein the above formulae    -   R₂ and R₃ independently of one another are C₁-C₆alkyl,    -   R₄ is C₁-C₄alkyl; pentyl; hexyl or NR₇R₈,    -   R₅ and R₆ independently of one another are C₁-C₄alkyl,    -   R₇ and R₈ independently of one another are hydrogen or        C₁-C₄alkyl,    -   R₉ and R₁₀ independently of one another are unsubstituted        C₁-C₄alkyl or C₁-C₄alkyl substituted by at least one substituent        chosen from the group consisting of hydroxyl, cyano, carboxyl,        SO₃H, —NH₂, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and        pyridyl,    -   u is from 1 to 6,    -   A₁ is a unit which completes an pyrrole-; imidazol-; pyridine-;        pyrazine-; pyrimidine-; pyridazine-ring, and    -   B₁ is a unit which completes a morpholino-; pyrrolidine-;        piperazine- or piperidine-ring,

-   each Q₂ is independently from each other hydroxyl; C₁-C₁₀alkyl;    branched C₃-C₁₀alkyl; C₂-C₁₀alkenyl; branched C₃-C₁₀alkenyl and    mixtures thereof; C₁-C₁₀alkoxy; a sulfo or carboxyl radical; a    radical of the formula

-    a branched alkoxy radical of the formula

an alkylethyleneoxy unit of the formula-(T₁)_(d)-(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of the formula COOR₁₈,

-   -   in which    -   B₂ is hydrogen; hydroxyl; C₁-C₁₈alkyl; C₁-C₁₈alkoxy; —CO₂H;        —CH₂COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁; —PO₃ ²⁻M₁; —OPO₃ ²⁻M₁; and        mixtures thereof,    -   B₃ is hydrogen; hydroxyl; —COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁ or        C₁-C₄alkoxy,    -   M₁ is hydrogen; alkalimetal-ion or an ammonium ion,    -   T₁ is —O— or —NH—,    -   X₁ and X₄ independently of one another are —O—; —NH— or        —N(C₁-C₄alkyl)-,    -   R₁₁ and R₁₂ independently of one another are hydrogen; a sulfo        group and salts thereof; a carboxyl group and salts thereof or a        hydroxyl group; at least one of the radicals R₁₁ and R₁₂ being a        sulfo or carboxyl group or salts thereof,    -   Y₂ is —O—; —S—; —NH— or —N(C₁-C₄alkyl)-,    -   R₁₃ and R₁₄ independently of one another other are hydrogen;        C₁-C₄alkyl; hydroxy-C₁-C₄alkyl; cyano-C₁-C₄alkyl;        sulfo-C₁-C₄alkyl; carboxy or halogen-C₁-C₄alkyl; unsubstituted        phenyl or phenyl substituted by at least one substitutent chosen        from the group consisting of halogen, C₁-C₄alkyl and        C₁-C₄alkoxy; sulfo or carboxyl or R₁₃ and R₁₄ together with the        nitrogen atom to which they are bonded form a form morpholino,        piperazine or piperidine ring,    -   R₁₅ and R₁₆ independently of one another are C₁-C₄alkyl or        aryl-C₁-C₄alkyl radicals,    -   R₁₇ is hydrogen; an unsubstituted C₁-C₄alkyl or C₁-C₄alkyl        substituted by at least one substitutent chosen from the group        consisting of halogen, hydroxyl, cyano, SO₃H, —NH₂, phenyl,        carboxyl, carb-C₁-C₄alkoxy or C₁-C₆alkoxy,    -   R₁₈ is C₁-C₁₀alkyl; branched C₃-C₁₀alkyl; C₁-C₁₀alkenyl or        branched C₃-C₁₀alkenyl; C₃-C₂₂glycol; C₁-C₁₀alkoxy; branched        C₃-C₁₀alkoxy; and mixtures thereof,    -   M is hydrogen; Na⁺; K⁺ or an ammonium ion,    -   Z₂ ⁻ a is a alkanolate; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻; BF₄ ⁻;        PF₆ ⁻; R₀SO₃ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻; citrate ion;        tartrate ion or oxalate ion, wherein R₀ is hydrogen; or        unsubstituted C₁-C₁₈alkyl; or C₁-C₁₈alkyl, which is substituted        by at least one substituent chosen from the group consisting of        hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy,        C₁-C₆alkoxy, phenyl, naphthyl and pyridyl; unsubstituted aryl or        aryl, which is substituted by at least one substituent chosen        from the group consisting of hydroxyl, cyano, carboxyl, SO₃H,        —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy and C₁-C₄-alkyl,    -   a is 0 or 1,    -   b is from 0 to 6,    -   c is from 0 to 100,    -   d is 0; or 1,    -   e is from 0 to 22,    -   v is an integer from 2 to 12,    -   w is 0 or 1, and    -   A⁻ is an organic or inorganic anion, and    -   s is equal to r₂, r₃, r₄ and r₅ in cases of monovalent anions A⁻        and is ≦r₂, r₃, r₄ and r₅ in cases of polyvalent anions, it        being necessary for A₈, to compensate the positive charge;        where, when r₂, r₃, r₄ and r₅≠1, the radicals Q₁ can be        identical or different,

-   each L is independently from each other a direct bond; —SO₂—; —O—;    —OR₁₉—; —OR₁₉O—; —OR₁₉N(R₂₀)—; —N(R₂₀)—; —(CH₂CH₂O—)_(n)—; —C(O)—;    —C(O)N(R₂₀)—; —N(R₂₀)C(O)—; —OC(O)—; —C(O)O—; —S—; unsubstituted,    linear or branched C₁-C₁₈alkylene; linear or branched    C₁-C₁₈alkylene, which is substituted by at least one substituent    chosen from the group consisting of hydroxyl, cyano, SO₃H, —NH₂,    carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and    pyridyl; unsubstituted C₅-C₁₈arylene; C₅-C₁₈arylene, which is    substituted by at least one substituent chosen from the group    consisting of hydroxyl, cyano, carboxyl, carb-C₁-C₄alkoxy,    C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted, linear or branched    C₁-C₁₈alkylene-C₅-C₁₈aryl; linear or branched    C₁-C₁₈alkylene-C₅-C₁₈aryl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl,    phenyl, naphthyl and pyridyl; unsubstituted, linear or branched    C₅-C₁₈arylene-C₁-C₁₈alkyl or linear or branched    C₅-C₁₈arylene-C₁-C₁₈alkyl, which is substituted by at least one    substituent chosen from the group consisting of hydroxyl, cyano,    SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl,    phenyl, naphthyl and pyridyl, wherein    -   R₁₉ is unsubstituted, linear or branched C₁-C₁₈alkylene; linear        or branched C₁-C₁₈alkylene, which is substituted by at least one        substituent chosen from the group consisting of hydroxyl, cyano,        SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,        naphthyl and pyridyl; unsubstituted C₅-C₁₈arylene;        C₅-C₁₈arylene, which is substituted by at least one substituent        chosen from the group consisting of hydroxyl, cyano, SO₃H, —NH₂,        carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl;        unsubstituted, linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl;        linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl, which is        substituted by at least one substituent chosen from the group        consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,        carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and        pyridyl; unsubstituted, linear or branched        C₅-C₁₈arylene-C₁-C₁₈alkyl or linear or branched        C₅-C₁₈arylene-C₁-C₁₈alkyl, which is substituted by at least one        substituent chosen from the group consisting of hydroxyl, cyano,        carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl,        naphthyl and pyridyl,    -   R₂₀ is unsubstituted, linear or branched C₁-C₁₈alkyl; linear or        branched C₁-C₁₈alkyl, which is substituted by at least one        substituent chosen from the group consisting of hydroxyl, cyano,        SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl,        naphthyl and pyridyl; unsubstituted C₅-C₁₈aryl; C₅-C₁₈aryl,        which is substituted by at least one substituent chosen from the        group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl,        carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted,        linear or branched C₁-C₁₈alkoxy or linear or branched        C₁-C₁₈alkoxy, which is substituted by at least one substituent        chosen from the group consisting of hydroxyl, cyano, SO₃H, —NH₂,        carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and        pyridyl,    -   N is 1; 2; 3 or 4,

-   each D is independently from each other a dyestuff radical of    formula (I), (II), (III), (IV), (V), (VI), (VII), (VIII), (IX), (X),    (XI), (XII), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII), (XIX),    (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV), (XXVI), (XXVIIa),    (XXVIIb), (XXVIIc), (XXVIId), (XXVIII), (XXIX), (XXX), (XXXI),    (XXXII), (XXXIII), (XXXIV), (XXXV), (I′), (II′), (III′), (IV′),    (V′), (VI′), (VIIa′), (VIIb′), (VIII′), (IX′), (X′), (XI′), (XII′),    (XIII′), (XIV′), (XV′), (XVI′), (XVII′), (XVIII′), (XIX′), (XX′),    (XXI′), (XXVIIa′), (XXVIIb′), (XXVIIc′), (XXVIId′), (XXVIII′),    (XXIX′), (XXX′), (XXXI′), (XXXII′),

-   r₂ is 0 or 1,

-   r₃ is 0 or 1, and

-   r₄ is 0 or 1.

A further embodiment of the present invention relates to process ofproduction of the compounds of formula (1a) and (1b):

wherein X and X′ are a leaving group andall other substituents have the meaning as defined above.

For the synthesis of metal phthalocyanines, two different pathways maybe followed: either the initial synthesis of a metal-free phthalocyaninederivative and subsequent complexation with a metal salt or thesynthesis of a phthalocyanine ring system from a simple benzenoidprecursor by concomitant incorporation of the metal ion.

Substituents can be introduced before or after the formation of thephthalocyanine ring system. In the former case, this leads toderivatives with substituents in all four rings, whereas in the lattercase the degree of substitution will be variable.

By an introduction of suitable substituents, water-solublephthalocyanines can be obtained after known procedures (DE1569783,DE1569729, DE2021257, DE1794298). The synthesis and use of such metalphthalocyanines for the use as photoactivators are also known (DE0081462and references cited therein).

A suitable method to obtain water-soluble phthalocyanine is theintroduction of sulfonate groups. Generally, the sulfonatedphthalocyanines are not pure substances, but complex mixtures ofdifferent positional isomers. Also the degree of sulfonation is varyingand normally not whole-numbered. For example, a tetra sodium salt of theZinc phthalocyanine can be prepared after known procedure [J. Griffithset al., Dyes and Pigments, Vol 33, 65-78 (1997) and literature citedtherein].

In the present application, a water-soluble phthalocyanine molecule isbeing linked through covalent bonds with a dye molecule. A convenientway to realize this linkage is the synthesis of a metal phthalocyaninesulfonyl chloride by a sulfochlorination reaction after known procedures[DE2812261, DE0153278]. By varying the amount of the sulfochlorinationagent, the desired degree of sulfochloride content can be adjusted. Thesulfochlorination reaction of phthalocyanines generally leads to a mainproduct, but as by-products small amounts of lower or higher degree ofsulfonyl chloride groups are detected.

The resulting reactive phthalocyanine-sulfonylchloride can then bereacted further with a suitable dye having an amino group.

To illustrate the synthesis, the following synthetic examples leading toZinc and Aluminium Phtalocyanines linked with amino-functionalizedazo-dyes are given. The syntheses are performed as shown in thefollowing scheme. From the possible positional isomers, only one isshown. The formation of the side products (degree of SO₃R and SO₂Cl) isnot shown.

The following Examples serve to illustrate the invention but do notlimit the invention thereto. Parts and percentages relate to weight,unless otherwise indicated. Temperatures are in degrees Celsius, unlessotherwise indicated.

SYNTHESIS EXAMPLES General Procedures 1) Synthesis of a Sulfonated ZincPhthalocyanine Sulfonyl Chloride

Normally the sulfonated Zinc phthalocyanine tetrasulfonic acid sodiumsalt is a mixture of different isomers with an average degree ofsulfonation about 3.6-3.8. The main components are various isomers oftetrasulfonated and trisulfonated Zinc phthalocyanines. Before thereaction, the material must be dried by freeze drying or spray drying.The dried Zinc phthalocyanine tetrasulfonic acid sodium salt (1 mol) isslowly added under stirring to chlorosulfuric acid (3.5 mol) at roomtemperature. The reaction mixture is heated at 90-95° C. for 30 minutes.At this temperature a certain amount of thionyl chloride (1.5 mol) isadded dropwise. If the sulfonated Zinc phthalocyanine tetrasulfonic acidsodium salt contains considerable amounts of water (determinationaccording the Karl-Fischer method), more thionyl chloride (up to 8 mol)must be added. Stirring is continued for another 90 minutes at 90° C.The reaction mixture is cooled down to room temperature and added to anexcess of ice. The formed green precipitate is filtered off, washed withaqueous sodium chloride (3%) and dried. The crude green intermediate isdirectly used for the next reaction step.

2) Synthesis of a Zinc Phthalocyanine Dye Conjugate

To an aqueous stirred solution of the corresponding dye (0.35 mol) isadded the Zinc phthalocyanine sulfonyl chloride prepared in example 1.During the addition, pH is adjusted to 7 with aqueous solution of sodiumhydroxide. The reaction mixture is reacted at pH 7 for 8 hours at roomtemperature. The reaction control is done by TLC (solvent pyridine 25ml/N,N-diethyl amine 33 ml/3-methylbutanol/aqueous ammonia (25%) 25 ml).When no starting dye can be detected, the reaction solution isworked-up.

Work-Up and Purification:

The reaction mixture is desalted by dialysis (cellulose tubes) or bynanofiltration through a suitable membrane. The desalted reactionsolution contains the isomeric mixture of covalently linked sulfonatedZinc phthalocyanine dye conjugates and starting material (Zincphthalocyanine tetrasulfonic acid). The obtained blue reaction solutioncan be directly used for the synthesis of liquid or solid formulations.

A solid Zinc phthalocyanine dye conjugate can be obtained byfreeze-drying the desalted solution.

Because there are a lot of possible isomers with regard to the positionof the sulfonic acid group and the sulfonamide linkage, the idealizedstructures are given.

The sulfonic acid functions can exist in the free acid form or as in thesodium salt form or as a mixture thereof.

Example 1 1. a) Synthesis of Zinc Phthalocyanine Monosulfonyl Chloride

138.6 g Zinc phthalocyanine tetrasulfonic acid sodium salt, 337 mlchlorosulfuric acid and 16 ml of thionylchloride are reacted as given inthe general procedure. The reaction mixture is given onto 300 g of ice.The precipitate is isolated as described above.

Yield: 696.5 g, green humid solid.

b) Synthesis of a Zinc Phthalocyanine Bisazo Dye Conjugate

To a solution of 1.7 g dye (prepared according to known procedures bydiazotation of commercially available 4-amino-azobenzol-4′-sulfonic acidand subsequent coupling to J-acid) in 25 ml destined water is addedunder stirring 6.4 g of crude Zinc phthalocyanine monosulfonyl chloridefrom example 1a. The reaction mixture is diluted with 15 ml destinedwater. A pH value of 6.1 of the reaction mixture is adjusted by additionof 1 N sodium hydroxide solution. The reaction is stirred for 10 hoursat room temperature. After the reaction is complete (TLC control withsolvent mixture pyridine 12.5 ml/N,N-diethylamine 16.6ml/3-methylbutanol 8.3 ml, aqueous ammonia 25% 12.5 ml), the product isprecipitated with a mixture of 400 ml of an aqueous (1.5%) sodiumchloride solution and 30 ml isopropanol. The crude dark blue reactionproduct is filtered off and dried at room temperature. The purificationstep (precipitation with sodium chloride solution/isopropanol) isrepeated twice to obtain a pure product.

Yield: 1.2 g (48%), violet solid.

Alternatively, the purification can be done by chromatography. Thereaction mixture is concentrated in vacuum and the crude product cleanedby thin layer chromatography (silicagel, solvent mixture as givenabove).

The substance is characterized by liquid chromatography in combinationwith UV absorption studies (LC-UV) and mass spectroscopy.

UV spectra: λ_(max) 520 and 670 nm.

M⁺ (MALDI-TOF): 1409 (M++H⁺). Assignment of fragments are listed in thefollowing table.

mass fragment 1135

1054

Example 2 Synthesis of a Zinc Phthalocyanine Bisazo Dye Conjugate

184.8 g of a commercial available aqueous solution of Direct Violet 99(trade name: Pontamine Brilliant Violet, dye concentration around 10%)is diluted with 1.51 water. In this dye solution, 696.5 g sulfonatedZinc phthalocyanine monosulfonylchloride from example 1a is added andreacted as described in the general procedure. After 12 h stirring atroom temperature the reaction is complete. The aqueous solution isdesalted by dialysis (cellulose tube, Fisherbrand, MWCO 12.000-14.000).After 12 h of dialysis, the amount of chloride and sulfat salts ischecked. Normally dialysis is complete, otherwise dialysis must becontinued for 20 hours. The obtained solution is freeze-dried to get ablue solid.

UV-spectra λ_(max) 340, 540, 670 nm

¹H NMR (DMSO-d₆) δ=15.99 (Ar—OH), 11.50 (SO2-NH-dye), 9.3-10.0 (aromatichydrogens), 8.0-9.0 (aromatic hydrogens), 7.45 (aromatic hydrogens),4.02 (OCH₃ ), 2.69 (ArCH₃ ) ppm.

Molecular formula (Idealized structure given above, free acid form)C₆₀H₃₇N₁₃O₂₂S₇Zn (1581.9).

MS (ESI) m/z 448 [M-2H]²⁻, tetrasulfonated Zn pc (Zinc phthalocanine),897 [M-H]¹⁻, tetrasulfonated Zn pc, 817, 407, 1225 (trisulfonated Znpc), 789 [M-2H]²⁻, tetrasulfonated Zn pc dye conjugate, 749 ([M-2H]²⁻trisulfonated Zn pc dye conjugate).

The Zinc phthalocyanine dye conjugates contains considerable amounts ofstarting material, therefore the resulting mixture can be described withthe following general formula:

Formula of the resulting mixture:C₄₆H_(21.8)N_(10.5)ZnNa_(4.7)O_(16.1)S_(5.2) (1318.3)

The dye conjugate contained 14.8% water.

Elemental analysis: C_(calc.) 35.6%, C_(found) 36.20%.

Example 3 Synthesis of a Zinc Phthalocyanine Bisazo Dye Conjugate

687 mg Zinc phthalocyanine tetrasulfonic acid sodium salt, 1.67 mlchlorosulfuric acid and 78.5 μl of thionylchloride are reacted andworked-up as given in the general procedure. The dye component issynthesized by a known procedure. As first step2-naphthylamino-4,8-disulfonic acid (C-acid) is diazotized and coupledwith 2-(2-amino-4-methylphenoxy)ethanol. This intermediate is againdiazotized and coupled with 2-amino-5-naphthol-7-sulfonic acid (J-acid).

128 mg of the violet dye is dissolved in 15 ml of water and reacted withthe crude Zinc-phthalocyanine sulfonylchloride according to the generalprocedure. The obtained solution is freeze-dried to get a blue solid.

Example 4 Synthesis of a Zinc Phthalocyanine Bisazo Dye Conjugate

687 mg Zinc phthalocyanine tetrasulfonic acid sodium salt is activatedto the Zinc phthalocyanine sulfonylchloride as described in the generalprocedure.

The used dye is prepared by a diazotization/coupling procedure startingfrom sulfanilic acid and 1-naphthylamine-6-sulfonic acid (1,6-Cleveacid). This intermediate is diazotized and coupled with J-acid.

115 mg of violet dye is dissolved in 15 ml of water and reacted with thecrude Zinc-phthalocyanine sulfonylchloride according to the generalprocedure. The obtained solution is freeze-dried to get a blue solid.

Example 5 Synthesis of a Zinc Phthalocyanine Bisazo Dye Conjugate

7.6 g Zinc phthalocyanine tetrasulfonic acid sodium salt is activated tothe Zinc phthalocyanine sulfonylchloride as described in the generalprocedure.

The violet dye is prepared after known procedures by diazotization andcoupling of 2-naphthylamino-6,8-disulfonic acid (amino-G-acid) to2-(2-amino-4-methylphenoxy)ethanol. The intermediate is subsequentlycoupled with J-acid.

To an aqueous solution of 1.5 g dye in 45 ml of water is added the crudeZinc phthalocyanine sulfonyl chloride and reacted as described in thegeneral procedure.

Work-up: The crude Zinc phthalocyanine dye conjugate is isolated by amixture of aqueous of sodium chloride (1.5%) and isopropanol.

Yield: 8 g crude dye, blue solid.

Example 6 Synthesis of a Zinc Phthalocyanine Bisazo Dye Conjugate

2.5 g Zinc phthalocyanine tetrasulfonic acid sodium salt is activated tothe sulfonylchloride as described in example 3.

The violet dye is prepared according to known procedures bydiazotization and coupling of 5-amino-salicylic acid to2-(2-amino-4-methylphenoxy)ethanol. The intermediate is subsequentlycoupled to J-acid.

To a solution of 400 mg dye in 25 ml water is added the crude Zincphthalocyanine sulfonylchloride and reacted as described in the generalprocedure. Work-up is done according to example 5.

Yield: 2 g Zinc phthalocyanine dye conjugate, blue solid.

Example 7 Synthesis of a Zinc Phthalocyanine Mono Azo Dye Conjugate

3.84 g Zinc phthalocyanine tetrasulfonic acid sodium salt is activatedto the sulfonylchloride and isolated as described in the generalprocedure.

To a solution of 555 mg of the dye component (prepared according toknown procedures by the reaction of 4-nitroaniline-2-sulfonic acid andsulfo-γ-acid and subsequent reduction) in 15 ml of water the crudeZinc-phthalocyanine sulfonylchloride is added and reacted according tothe general procedure. The obtained solution is freeze-dried to get ablue solid.

Example 8 Synthesis of a Zinc Phthalocyanine Mono Azo Dye Conjugate

3.84 g Zinc phthalocyanine tetrasulfonic acid sodium salt is activatedto the Zinc phthalocyanine sulfonylchloride and isolated as described inthe general procedure. The crude Zinc phthalocyanine sulfonylchloride isadded to a solution of 469 mg of the dye (prepared according to knownprocedures by the reaction of 4-nitroaniline-2-sulfonic acid and γ-acidfollowed by subsequent reduction) in 15 ml of water and reacted asdescribed in the general procedure. The obtained solution isfreeze-dried to get a blue solid.

Example 9 Synthesis of a Zinc Phthalocyanine Bis Azo Dye Conjugate

1.44 g Zinc phthalocyanine tetrasulfonic acid sodium salt is activatedto the Zinc phthalocyanine sulfonylchloride and isolated as described inthe general procedure. The crude Zinc-phthalocyanine sulfonylchloride isadded to a solution of 751 mg dye (prepared according to knownprocedures by the diazotation and coupling reaction of sulfanilic acidand 3-amino-acetanilide-4-sulfonic acid to H-acid followed by a finalsaponificaton step) in 15 ml of water. The reaction is done according tothe general procedure. The obtained solution is freeze-dried to get ablue solid.

Example 10 Synthesis of a Zinc Phthalocyanine Mono Azo Dye Conjugate

3.84 g Zinc phthalocyanine tetrasulfonic acid sodium salt is activatedto the Zinc phthalocyanine sulfonylchloride and isolated as described inthe general procedure. The crude Zinc phthalocyanine sulfonylchloride isadded to a solution of 485 mg of dye (prepared according to a knownprocedure by a diazotation and coupling reaction of4-methoxy-aniline-2-sulfonic acid to J-acid) in 15 ml of water. Thesolution is reacted and worked-up as described in the general procedure.The obtained solution is freeze-dried to get a blue solid.

Example 11 Synthesis of a Zinc Phthalocyanine Mono Azo Dye Conjugate

3.84 g Zinc phthalocyanine tetrasulfonic acid sodium salt is activatedto the sulfonylchloride and isolated as described in the generalprocedure.

The crude Zinc phthalocyanine sulfonylchloride is added to a solution of539 mg of the dye (prepared according to known procedures by adiazotation and coupling reaction of aniline-2,5-disulfonic acid toJ-acid), reacted and worked-up as described in the general procedure.The obtained solution is freeze-dried to get a blue solid.

Example 12 a) Synthesis of Aluminium Phthalocyanine MonosulfonylChloride

2.63 g of sodium salt of Aluminium phthalocyanine tetrasulfonic acid isadded with stirring to 6.5 ml (95.6 mmol) chloro sulfuric acid at roomtemperature. The reaction mixture is heated at 90° C. for 20 minutes.Within 3 minutes, 313.8 μl of thionyl chloride are carefully addeddropwise. Stirring is continued for another 90 minutes at 90° C. Thereaction mixture is cooled down to room temperature and, with vigorousstirring, added to 20 g of ice. The formed precipitate is filtered off,washed with 1.5% aqueous NaCl solution (2×5 ml) and dried for 10 minuteswith a vacuum pump. The crude product (8.9 g, wet cake) is directly usedfor the next reaction step.

b) Synthesis of a Aluminium Phthalocyanine Bisazo Dye Conjugate

To a solution of 1.7 g Direct Red 254 dye in 25 ml destined water isadded under stirring 6.36 g of crude Aluminium phthalocyaninemonosulfonyl chloride from example 12a. The reaction mixture is dilutedwith 15 ml destined water. A pH value of 1.7 of the reaction mixture isadjusted by addition of 1 N sodium hydroxide solution (14 ml) to 9.6.The reaction is stirred for 0.5 hours at room temperature. pH is 9.4.Stirring is continued for 17 h at room temperature. TLC is recorded witha solvent mixture of pyridine 12.5 ml/N,N-diethylamine 16.6ml/isopropylalcohol 10.8 ml, aqueous ammonia 25% 10.1 ml). The productis precipitated with a mixture of 15 ml of an aqueous (3%) sodiumchloride solution and 200 ml isopropanol. The crude dark coloredreaction product is centrifuged for 10 min. at 1800 rpm. The stickysolid obtained is treated with ethyl acetate to get granular solid,which is dried under vacuum at room temperature.

Yield: 2.1 g, dark colored solid.

UV spectra: λ_(max) 295, 355, 509, 610 and 677 nm.

Example 13 Synthesis of a Aluminium Phthalocyanine Bisazo Dye Conjugate

To a solution of 0.8 g of Pontamine Brilliant BRW in 10 ml of destinedwater 2.57 g of Aluminium phthalocyanine monosulfonyl chloride fromexample 12a is slowly added under stirring. A pH value of 1.9 of thereaction mixture is adjusted by addition of 1 N sodium hydroxidesolution (6.5 ml) to 7.6. The reaction is stirred for 0.5 hours at roomtemperature. Stirring is continued for 17 h at room temperature. TLC isrecorded with a solvent mixture of pyridine 12.5 ml/N,N-diethylamine16.6 ml/isopropylalcohol 8.3 ml, aqueous ammonia 25% 12.5 ml). Work-upand purification (precipitation with sodium chloride/isopropanol) areaccomplished as described for example 3b.

Yield: 0.62 g, dark blue solid.

UV spectra: λ_(max) 296, 353, 609, and 676 nm. (Peak at 609 is embeddedin a hump which starts from 460 nm Ξ pontamine absorption maximum).

APPLICATION EXAMPLES Degradation Experiments

An aqueous solution of the photocatalyst was exposed in the givenconcentration in a closed 50 ml glass bottle to an optical illuminationunit (Leitz) equipped with a photooptic lamp Xenophot (Osram HLX 64625).The intensity measured with a Roline RO-1322 Digital Lux meter in frontof the bottle was within the range of 111000-120000 Lux.

The degradation of the photocatalyst was determined fromspectrophotometric data gained with a HP 8452 Diode arrayspectrophotometer. The absorption was measured at representativewavelengths of the chromophoric components of the photocatalyst. (670nm, 540 nm). While there is only a small overlap at the absorptionmaximum originating from the Phthalocyanine part (670 nm) of thephotocatalyst by the absorption of the attached dye-chromophore, theremay be an appreciable overlap at the absorption maximum of the attacheddyestuff chromophore itself, depending on its structure, by thePhthalocyanine part. The absorption was determined at the start and thenafter illumination every 5 respectively 10 min up to 2 hours. Thenormalized photochemical destruction of the photocatalyst, given as lossin percentage regarding the initial absorption at the selectedwavelength is summarized in table 1, covering an illumination period upto 2 hours

Example 14

An aqueous solution containing 60 mg/l of the blue photocatalystobtained from Example 2 was illuminated following the procedure outlinedabove. Upon illumination the photocatalyst was degraded to a high extentregarding both chromophoric parts.

TABLE 1 Loss of absorption in % upon illumination at relevant wavelengthof the chromophors Time in min 670 nm 540 nm 0 0.00% 0.00% 5 3.80% 2.01%10 9.78% 17.44% 15 14.40% 21.93% 20 18.68% 23.59% 25 23.28% 25.41% 3028.29% 29.89% 35 32.53% 31.31% 40 37.09% 32.14% 45 41.99% 36.40% 5046.63% 40.80% 55 54.55% 43.34% 65 59.57% 45.07% 75 66.45% 46.68% 8571.46% 49.56% 95 75.03% 49.33% 105 77.66% 49.50% 115 79.18% 49.85%

Example 15

An aqueous solution of the bluish photocatalyst obtained from Example 1containing 100 mg/l was illuminated following the procedure outlinedabove at neutral pH. Upon illumination the photocatalyst was degraded toa high extent.

TABLE 2 Loss of absorption in % upon illumination at relevant wavelengthof the chromophors Time in min 670 nm 514 nm 0 0.00% 0.00% 5 3.09% 2.00%10 5.92% 3.10% 15 9.24% 4.56% 20 12.52% 5.96% 25 15.80% 6.91% 30 18.95%8.07% 35 22.37% 9.21% 40 25.93% 10.91% 45 28.91% 12.14% 50 32.66% 13.76%60 37.77% 15.21% 70 43.07% 16.93% 80 47.59% 18.58% 90 51.28% 19.88% 10054.39% 20.85% 110 57.38% 21.79% 120 59.52% 22.63%

Example 16

An aqueous solution, adjusted to pH 11 containing 31 mg/l of the bluephotocatalyst obtained from Example 2 was illuminated following theprocedure outlined above. Upon illumination the photocatalyst wasdegraded to a very high degree regarding both chromophoric parts.

TABLE 3 Loss of absorption in % upon illumination at relevant wavelengthof the chromophors Time in min 670 nm 540 nm 0 0.00% 0.00% 5 8.58%11.54% 10 16.31% 20.17% 15 24.52% 27.93% 20 32.25% 36.26% 25 39.28%42.80% 30 45.97% 47.86% 35 51.90% 51.17% 40 57.49% 56.02% 45 62.27%58.61% 50 66.48% 61.30% 55 70.13% 63.45% 65 76.10% 67.58% 75 80.19%68.80% 85 83.15% 70.21% 95 85.28% 71.07%

Example 17

An aqueous solution containing 60 mg/l of the blue photocatalystobtained from Example 2 was illuminated at neutral pH following theprocedure outlined above. At neutral pH the compound is partiallyaggregated. Nevertheless upon illumination the photocatalyst wasdegraded to a high extent regarding both chromophoric parts.

TABLE 4 Loss of absorption in % upon illumination at relevant wavelengthof the chromophors Time in min 670 nm 540 nm 5 0.35% 12.12% 10 6.54%25.96% 15 11.33% 29.98% 20 15.77% 31.48% 25 20.53% 33.10% 30 25.72%37.12% 35 30.11% 38.40% 40 34.83% 39.14% 45 39.91% 42.97% 50 44.72%46.91% 60 52.92% 49.18% 70 58.12% perturbed 80 65.25% 52.18% 90 70.44%54.76% 100 74.14% 54.56% 110 76.86% 54.71% 120 78.44% perturbed

TABLE 5 Loss of absorption in % upon illumination at relevant wavelengthof the chromophors pH neutral Results with Zn-pc dye conjugate ofexample 3 Time in min 670 nm 540 nm 0 0.00% 0.00% 5 4.71% 2.23% 1010.24% 3.96% 15 15.51% 5.68% 20 21.50% 7.53% 25 27.33% 9.11% 30 33.08%10.99% 35 38.16% 12.39% 40 42.87% 14.02% 45 47.58% 14.45% 50 51.13%16.32% 60 56.08% 18.07% 70 59.56% 20.18% 80 61.72% 20.46% 90 64.05%21.43% 100 64.91% 22.37% 110 65.68% 22.74% 120 65.85% 24.46%

TABLE 6 Loss of absorption in % upon illumination at relevant wavelengthof the chromophors pH neutral Results with Zn-pc dye conjugate ofexample 4 Time in min 670 nm 540 nm 0 0.00% 0.00% 5 8.57% 6.53% 1017.65% 8.97% 15 24.81% 9.42% 20 31.45% 9.12% 25 38.26% 12.90% 30 44.11%13.46% 35 49.20% 15.15% 40 53.70% 16.11% 45 57.74% 16.34% 50 61.09%17.95% 60 66.57% 19.75% 70 70.20% 19.83% 80 73.22% 24.30% 90 74.05%24.56% 100 75.92% 24.02% 110 76.61% 23.45% 120 77.42% 25.87%

TABLE 7 Loss of absorption in % upon illumination at relevant wavelengthof the chromophors pH neutral Results with Zn-pc dye conjugate ofexample 5 Time in min 670 nm 540 nm 0 0.00% 0.00% 5 6.81% 3.13% 1015.08% 6.09% 15 22.99% 9.09% 20 31.61% 10.70% 25 39.06% 14.66% 30 47.01%19.28% 35 53.57% 21.25% 40 59.19% 22.96% 45 63.20% 23.84% 50 67.61%24.60% 60 73.87% 26.93% 70 78.10% 29.69% 80 80.64% 30.69% 90 82.29%31.48% 100 83.38% 32.45% 110 84.10% 33.37% 120 84.47% 33.53%

TABLE 8 Loss of absorption in % upon illumination at relevant wavelengthof the chromophors pH neutral Results with Zn-pc dye conjugate ofexample 6 Time in min 670 nm 540 nm 0 0.00% 0.00% 5 6.54% 3.48% 1012.48% 6.01% 15 19.67% 9.33% 20 26.49% 12.19% 25 33.56% 14.92% 30 40.34%17.68% 35 45.46% 20.01% 40 50.65% 63.20% 45 55.41% 23.95% 50 59.80%25.33% 60 65.85% 27.66% 70 70.30% 29.70% 80 73.63% 31.06% 90 75.92%32.55% 100 77.52% 34.09% 110 78.50% 34.31% 120 79.23% 35.12%

TABLE 9 Loss of absorption in % upon illumination at relevant wavelengthof the chromophors pH neutral Results with Zn-pc dye conjugate ofexample 7 Time in min 670 nm 540 nm 0 0.00% 0.00% 5 5.22% 6.19% 1010.82% 13.36% 15 17.47% 20.85% 20 21.95% 25.66% 25 26.96% 31.32% 3032.18% 34.99% 35 37.09% 37.80% 40 42.01% 41.58% 45 46.31% 45.26% 5050.59% 47.98% 60 57.78% 53.76% 70 63.76% 59.29% 80 68.57% 61.81% 9072.40% 64.46% 100 75.58% 67.10% 110 78.20% 69.16% 120 80.25% 70.23%

TABLE 10 Loss of absorption in % upon illumination at relevantwavelength of the chromophors pH neutral Results with Zn-pc dyeconjugate of example 8 Time in min 670 nm 540 nm 0 0.00% 0.00% 5 4.02%17.09% 10 11.25% 33.03% 15 17.99% 45.66% 20 24.68% 54.07% 25 29.25%60.04% 30 35.17% 65.61% 35 39.64% 69.32% 40 44.23% 72.83% 45 48.51%75.54% 50 51.91% 77.74% 60 58.06% 80.81% 70 63.11% 83.25% 80 67.29%84.85% 90 70.31% 85.62% 100 72.86% 87.27% 110 74.90% 87.69% 120 76.67%88.34%

TABLE 11 Loss of absorption in % upon illumination at relevantwavelength of the chromophors pH neutral Results with Zn-pc dyeconjugate of example 9 Time in min 670 nm 540 nm 0 0.00% 0.00% 5 3.97%0.76% 10 9.36% 1.93% 15 14.32% 2.63% 20 18.89% 4.10% 25 22.68% 4.93% 3026.59% 5.84% 35 30.69% 6.74% 40 33.89% 7.44% 45 37.21% 8.17% 50 39.80%8.27% 60 44.23% 8.56% 70 47.61% 8.48% 80 50.84% 9.46% 90 53.43% 10.36%100 55.25% 11.13% 110 57.31% 11.82% 120 58.69% 12.34%

Example 18

As comparison an aqueous solution, containing only the azo dye part ofthe blue photocatalyst was illuminated at neutral pH following theprocedure outlined above. No degradation of the chromophore was observedwithin two hours exposure.

Experiments with Fabrics

Example 19

A bleached cotton fabric was treated with an aqueous solution whichresulted in a bluish color. This fabric was exposed in a wet state forup to 90 min to a tungsten lamp. The light intensity measured with aRoline RO-1322 Digital Lux meter at the position of the fabric waswithin the range of 17000 Lux. The intensity of the blue color of thefabric was continuously reduced on exposure.

Washing Experiments

Bleached cotton was washed with a detergent containing the photocatalystobtained from Example 2 in different concentrations for 15 min at 30° C.

Detergent 40 gr/kg of fabricLiquor ratio 1:10

After washing one part of the fabrics were exposed to tungsten light fortwo hours (Light intensity measured with a Roline RO-1322 Digital Luxmeter at the position of the fabric was within the range of 17000 Lux.)one part was dried in the dark.

This washing cycle was repeated five times and after each washing cyclethe Whiteness (Ganz) and the tint value determined

Example 20

As reference one set of fabrics was washed with the detergent containinga commercial photocatalyst Tinolux BMC.

Concentration of photocatalyst in the detergent was 0.04%.

Example 21

The detergent used for the washing experiment contained an equivalent of0.01% of the blue photocatalyst obtained from Example 2.

Example 22

The detergent used for the washing experiment contained an equivalent of0.015% of the blue photocatalyst obtained from Example 2.

Example 23

The detergent used for the washing experiment contained an equivalent of0.009% of the blue photocatalyst obtained from Example 2.

The fabric was washed five time times without intermediate exposure tolight. After the five washes the fabric was exposed either in dry or wetstate for two hours to tungsten light.

Example 24

The detergent used for the washing experiment contained an equivalent of0.009% of the blue photocatalyst obtained from Example 2 andadditionally 0.01% Tinopal CBS (FWA of Ciba Specialty Chemicals).

The fabric was washed five time times without intermediate exposure tolight. After the five washes the fabric was exposed either in dry or wetstate for two hours to tungsten light.

The results of the shade and whiteness evaluation with and withoutexposure of the fabrics to light are summarized in table 12.

From the reflection spectra it could be derived that the buildup of thephotocatalyst BCF obtained from Example 2 was higher than for theturquoise reference photocatalyst Tinolux BMC.

The values in table 12 show the increased whiteness gained by the blueobtained from Example 2 in comparison to the reference photocatalyst andthe control to prevent overhueing by exposure to light while maintainingan appreciable gain in whiteness delivery.

TABLE 12 Whiteness (Ganz) and Tint Value (TV) of cotton fabrics washedwith detergent as exemplified above After After After After After 1 2 34 5 cycle cycles cycles cycles cycles W TV W TV W TV W TV W TV Withoutexposure to light Example 20 79 1.3 81 2.1 82 2.6 83 3.2 83 3.6 Example21 84 1.6 90 2.4 94 3.0 100 3.6 105 4.2 Example 22 88 2.3 98 4.0 106 5.1113 5.8 117 6.4 Example 23 99 3.58 Example 24 226 1.76 With exposure tolight Example 20 79 0.3 79 0.4 80 0.5 81 0.7 79 0.8 Example 21 80 0.3 830.4 86 0.7 89 0.9 91 1.3 Example 22 81 0.3 87 0.7 91 1.1 100 2.0 99 2.1Example 23 93 2.47 dry Example 23 97 1.76 wet Example 24 215 0.85 dryExample 24 217 0.44 wet

Photo-Bleaching Experiments on Soiled Fabrics Washing Procedure, LightExposure

A mixture of cotton soiled with red wine (testfabric No 114 of EMPA) andbleached cotton as ballast was washed under the condition as outlinedunder washing experiments. After five washing cycles the fabric wasexposed in wet state under the illumination conditions as outlined inexample 19. The lightness of the fabrics was evaluated as function ofexposure time.

The difference of the lightness between the fabrics after washing andafter exposure to light is a measure for the photobleaching performanceof the detergent containing the photocatalyst. The results aresummarized in table 13.

Example 25

As reference one set of fabrics was washed with the detergent containing0.04% of the commercial photocatalyst Tinolux BMC

Example 26

The set of fabrics was washed with a detergent containing 0.007% of thephotocatalyst of example 2

Example 27

The set of fabrics was washed with a detergent containing 0.0079% of thephotocatalyst of example 6.

Example 28

The set of fabrics was washed with a detergent containing 0.011% of thephotocatalyst of example 5.

TABLE 13 Delta Lightness Y (Lightness of soiled fabrics exposed after xhours illumination − Lightness of fabric after five washes) Hours ofexposure 1 h 2 h 6 h Example 25 4.1 4.2 5.1 Example 26 3.9 4.9 6.6Example 27 4.1 5.9 8.4 Example 28 4.4 5.7 7.5

1. A shading process for textile fiber material characterized by treating the textile fiber material with a composition comprising at least one Zn-, Ca-, Mg-, Na-, K-, Al, Si-, Ti-, Ge-, Ga-, Zr-, In- or Sn-phthalocyanine to which at least one dyestuff is attached through covalent bonding.
 2. A shading process according to claim 1, wherein the textile is treated with a composition comprising at least one compound of formula (1a) and/or formula (1b)

wherein PC is the phthalocyanine ring system, Me is Zn; Ca; Mg; Na; K; A₁-Z₁; Si(IV)-(Z₁)₂; Ti(IV)-(Z₁)₂; Ge(IV)-(Z₁)₂; Ga(III)-Z₁; Zr(IV)-(Z₁)₂; In(III)-Z₁ or Sn(IV)-(Z₁)₂, Z₁ is an alkanolate ion; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; R₀SO₃ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻; citrate ion; tartrate ion or oxalate ion, wherein R₀ is hydrogen; or unsubstituted C₁-C₁₈alkyl; or C₁-C₁₈alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy, phenyl, naphthyl and pyridyl; unsubstituted aryl or aryl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy and C₁-C₄-alkyl, r is 0; 1; 2; 3 or 4, r′ is 1; 2; 3 or 4, each Q₁ is independently of each other a sulfo or carboxyl group or a radical of the formula —SO₂X₂—R₁—X₃ ⁺; —O—R₁—X₃ ⁺ or —(CH₂)_(t)—Y₁ ⁺, in which R₁ is a branched or unbranched C₁-C₈alkylene; 1,3-phenylene or 1,4-phenylene, X₂ is —NH— or —N(C₁-C₅alkyl)-, X₃ ⁺ is a group of the formula

or, in the case where R₁=C₁-C₈alkylene, also a group of the formula

Y₁ ⁺ is a group of the formula

t is 0 or 1, wherein the above formulae R₂ and R₃ independently of one another are C₁-C₆alkyl, R₄ is C₁-C₆alkyl; C₅-C₇cycloalkyl or NR₇R₈, R₅ and R₆ independently of one another are C₁-C₅alkyl, R₇ and R₈ independently of one another are hydrogen or C₁-C₅alkyl, R₉ and R₁₀ independently of one another are unsubstituted C₁-C₆alkyl or C₁-C₆alkyl substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy, phenyl, naphthyl and pyridyl, u is from 1 to 6, A₁ is a unit which completes an aromatic 5- to 7-membered nitrogen heterocycle, which may where appropriate also contain one or two further nitrogen atoms as ring members, and B₁ is a unit which completes a saturated 5- to 7-membered nitrogen heterocycle, which may where appropriate also contain 1 to 2 nitrogen, oxygen and/or sulfur atoms as ring members, each Q′ is independently from each other a moiety of formula -L-D, wherein L is a direct bond or a bridging group and D is the radical of a dyestuff, each Q₂ is independently from each other hydroxyl; C₁-C₂₂alkyl; branched C₃-C₂₂alkyl; C₂-C₂₂alkenyl; branched C₃-C₂₂alkenyl and mixtures thereof; C₁-C₂₂alkoxy; a sulfo or carboxyl radical; a radical of the formula

 a branched alkoxy radical of the formula

 an alkylethyleneoxy unit of the formula -(T₁)_(d)-(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of the formula COOR₁₈, in which B₂ is hydrogen; hydroxyl; C₁-C₃₀alkyl; C₁-C₃₀alkoxy; —CO₂H; —CH₂COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁; —PO₃ ²⁻M₁; —OPO₃ ²⁻M₁; and mixtures thereof, B₃ is hydrogen; hydroxyl; —COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁ or C₁-C₆alkoxy, M₁ is a water-soluble cation, T₁ is —O— or —NH—, X₁ and X₄ independently of one another are —O—; —NH— or —N(C₁-C₅alkyl)-, R₁₁ and R₁₂ independently of one another are hydrogen; a sulfo group and salts thereof; a carboxyl group and salts thereof or a hydroxyl group; at least one of the radicals R₁₁ and R₁₂ being a sulfo or carboxyl group or salts thereof, Y₂ is —O—; —S—; —NH— or —N(C₁-C₅alkyl)-, R₁₃ and R₁₄ independently of one another other are hydrogen; C₁-C₆alkyl; hydroxy-C₁-C₆alkyl; cyano-C₁-C₆alkyl; sulfo-C₁-C₆alkyl; carboxy or halo-C₁-C₆alkyl; unsubstituted phenyl or phenyl substituted by at least one substituent selected from the group consisting of halogen, C₁-C₄alkyl, C₁-C₄alkoxy, sulfo or by carboxy; or R₁₈ and R₁₉, together with the nitrogen atom to which they are bonded, form a saturated 5- or 6-membered heterocyclic ring that may in addition contain a further nitrogen atom or an oxygen atom as ring member, R₁₅ and R₁₆ independently of one another are C₁-C₆alkyl or aryl-C₁-C₆alkyl radicals, R₁₇ is hydrogen; an unsubstituted C₁-C₆alkyl or C₁-C₆alkyl substituted by at least one substituent selected from the group consisting of halogen, hydroxyl, cyano, SO₃H, —NH₂, phenyl, carboxyl, carb-C₁-C₆alkoxy and C₁-C₆alkoxy, R₁₈ is C₁-C₂₂alkyl; branched C₃-C₂₂alkyl; C₁-C₂₂alkenyl or branched C₃-C₂₂alkenyl; C₃-C₂₂glycol; C₁-C₂₂alkoxy; branched C₃-C₂₂alkoxy; and mixtures thereof, M is hydrogen; or an alkali metal ion or ammonium ion, Z₂ is a is an alkanolate ion; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; R₀SO₃ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻; citrate ion; tartrate ion or oxalate ion, wherein R₀ is hydrogen; or unsubstituted C₁-C₁₈alkyl; or C₁-C₁₈alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy, phenyl, naphthyl and pyridyl; unsubstituted aryl or aryl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy and C₁-C₄-alkyl, a is 0 or 1, bis from 0 to 6, c is from 0 to 100, d is 0 or 1, e is from 0 to 22, v is an integer from 2 to 12, w is 0 or 1, and A⁻ is an organic or inorganic anion, and s is equal to r in cases of monovalent anions A⁻ and is less than or equal to r in cases of polyvalent anions, it being necessary for A_(s) ⁻ to compensate the positive charge; where, when r≠1, the radicals Q₁ can be identical or different, and where the phthalocyanine ring system may also comprise further solubilising groups.
 3. A process according to claim 2, wherein D is the radical of a azo-; diazo-; trisazo-, polyazo-; azomethin-; methin-; anthrachino-; dioxazine-; phenazine-; diphenylmethane-; triphenylmethane-; carbonyl-; xanthene-; acid- or thioxanthene-dyestuff.
 4. A process according to claim 1, wherein the composition comprising at least one compound of formula (1a) and/or (1b) produces a relative hue angle of 220-3200 and the compounds of formula (1a) and (1b) are not light stable.
 5. A process according to claim 4, wherein the decrease rate of the compounds of formula (1a) and/or (1b) is at least 1% per 2 hours, preferably at least 2% when the composition is exposed to (sun)light.
 6. A process according to claim 2 wherein D is a radical of formulae (I)-(XXXII):

wherein * marks the bond to the bridging group L, X and Y independently of one another, are hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy; linear or branched, C₁-C₄-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; NHCOOH; NHCOOC₁-C₄alkyl; COOH or COOC₁-C₄alkyl; U is a moiety of formula

R_(α) is hydrogen; linear or branched, unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; unsubstituted aryl or aryl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl, each R_(β) independently of one another is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy or linear or branched, C₁-C₄-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl, Z is linear or branched, unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy or linear or branched, C₁-C₄-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; halogen; OH; NO₂; COOH; COOC₁-C₄alkyl; NH₂; NHC₁-C₄alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH₂, C₁-C₄alkyl, CN and COOH; N(C₁-C₄alkyl)C₁-C₄alkyl, wherein the alkyl groups may independently of each other be substituted by at least one substituent selected from the group consisting of OH, NH₂, C₁-C₄alkyl, CN and COOH; NH-aryl; NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl and C₁-C₄alkoxy; NHCOC₁-C₄alkyl and NHCOOC₁-C₄alkyl, Z′ is SO₃M; linear or branched, unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy or linear or branched, C₁-C₄-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; halogen; OH; NO₂; COOH; COOC₁-C₄alkyl; NH₂; NHC₁-C₄alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH₂, C₁-C₄alkyl, CN or COOH; N(C₁-C₄alkyl)C₁-C₄alkyl, wherein the alkyl groups may independently of each other be substituted by at least one substituent selected from the group consisting of OH, NH₂, C₁-C₄alkyl, CN and COOH; NH-aryl; NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl and C₁-C₄alkoxy; NHCOC₁-C₄alkyl or NHCOOC₁-C₄alkyl, Z₁ is linear or branched, unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy or linear or branched, C₁-C₄-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; halogen; OH; NO₂; COOH; COOC₁-C₄alkyl; NH₂; NHC₁-C₄alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH₂, C₁-C₄alkyl, CN or COOH; N(C₁-C₄alkyl)C₁-C₄alkyl, wherein the alkyl groups may independently of each other be substituted by at least one substituent selected from the group consisting of OH, NH₂, C₁-C₄alkyl, CN and COOH; NH-aryl; NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl and C₁-C₄alkoxy; NHCOC₁-C₄alkyl or NHCOOC₁-C₄alkyl, Z₂, Z₃, Z₄, Z₅ and Z₆ are independently from each other hydrogen; linear or branched, unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy or linear or branched, C₁-C₄-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; halogen; OH; SO₂CH₂CH₂SO₃H; NO₂; COOH; COOC₁-C₄alkyl; NH₂; NHC₁-C₄alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH₂, C₁-C₄alkyl, CN or COOH; N(C₁-C₄alkyl)C₁-C₄alkyl, wherein the alkyl groups may independently of each other be substituted by at least one substituent selected from the group consisting of OH, NH₂, C₁-C₄alkyl, CN and COOH; NH-aryl; NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl and C₁-C₄alkoxy; NHCOC₁-C₄alkyl or NHCOOC₁-C₄alkyl, G is a direct bond; COOC₁-C₄alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; or —CO-arylene, n is 0; 1; 2 or 3, n′ is 0; 1 or 2, n″ is 0 or 1, m is 0; 1 or 2, m¹ is 0; 1 or 2, each M is independently from each other hydrogen; an alkali metal ion or an ammonium ion.
 7. A process according to claim 2 wherein D is a radical of formulae (I′)-(XXXII′):

wherein X and Y independently of one another are linear or branched, unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy, Z is unsubstituted C₁-C₂-alkyl; C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy; OH; NO₂; COOH; COOC₁-C₂alkyl, Z₁ is halogen; OH; NO₂; COOH or COOC₁-C₄alkyl, G is a direct bond; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 0; 1 or 2, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein X and Y independently of one another are linear or branched, unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy, Z is unsubstituted C₁-C₂-alkyl; C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy; OH; NO₂; COOH; COOC₁-C₂alkyl, Z₁ is OH; NO₂; COOH or COOC₁-C₂alkyl, G is a direct bond; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 0; 1 or 2, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein X and Y independently of one another are linear or branched, unsubstituted C₁-C₄-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy, Z is unsubstituted C₁-C₂-alkyl; C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy; OH; NO₂; COOH; COOC₁-C₂alkyl, Z₁ is OH; NO₂; COOH or COOC₁-C₄alkyl, G is a direct bond; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 0; 1 or 2, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein Z is unsubstituted C₁-C₂-alkyl; C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy; OH; NO₂; COOH; COOC₁-C₂alkyl, Z₁ is OH; NO₂; COOH or COOC₁-C₂alkyl, G is a direct bond or COOC₁-C₂alkylene, n is 0; 1 or 2, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein Z is unsubstituted C₁-C₂-alkyl; C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy; OH; NO₂; COOH; COOC₁-C₂alkyl, G is a direct bond or COOC₁-C₂alkylene, n is 0; 1 or 2, n″ is 0 or 1, m is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein Z is unsubstituted C₁-C₂-alkyl; C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy; OH; NO₂; COOH; COOC₁-C₂alkyl, G is a direct bond or COOC₁-C₂alkylene, n is 0; 1 or 2, n″ is 0 or 1, m is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂, Y is SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂, Z is NH₂ or NHCOOC₁-C₄alkyl, Z₁ is OH or NHCOC₁-C₄alkyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl, n is 0; 1 or 2, n″ is 0 or 1, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂, Y is SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂, Z is NH₂ or NHCOOC₁-C₄alkyl, Z₁ is OH or NHCOC₁-C₄alkyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl, n is 1; 2 or 3, n″ is 0 or 1, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂, Y is SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂, Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of SO₃H, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and C₁-C₂alkoxy, Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 1; 2 or 3, n″ is 0 or 1, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂, Y is SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂, Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of SO₃H, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and C₁-C₂alkoxy, Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 1; 2 or 3, n″ is 0 or 1, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, Z is NH₂; NHCOC₁-C₄alkyl or NHCOOC₁-C₄alkyl, Z₁ is OH; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl and C₁-C₄alkoxy, G is a direct bond; COOC₁-C₄alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl, n is 1; 2 or 3, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, Z is NH₂; NHCOC₁-C₄alkyl or NHCOOC₁-C₄alkyl, Z₁ is OH; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl and C₁-C₄alkoxy, G is a direct bond; COOC₁-C₄alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl, n is 1; 2 or 3, n″ is 0 or 1, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, Z is NH₂; NHCOC₁-C₄alkyl or NHCOOC₁-C₄alkyl, Z₁ is OH; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl and C₁-C₄alkoxy, G is a direct bond; COOC₁-C₄alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl, n is 1; 2 or 3, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent G selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂, Y is SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, and —NH₂; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H and —NH₂, Z is NH₂; NHCOC₁-C₄alkyl or NHCOOC₁-C₄alkyl, Z₁ is OH; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl and C₁-C₄alkoxy, G is a direct bond; COOC₁-C₄alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted C₁-C₄alkylene or C₁-C₄-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl, n is 1; 2 or 3, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy; linear or branched, C₁-C₄-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; COOH or COOC₁-C₂alkyl, Y is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy; linear or branched, C₁-C₄-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; COOH or COOC₁-C₂alkyl, Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and C₁-C₂alkoxy, Z′ is SO₃M; COOH or COOC₁-C₂alkyl, Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 1; 2 or 3, n′ is 0 or 1, n″ is 0 or 1, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy; linear or branched, C₁-C₄-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; COOH or COOC₁-C₂alkyl, Y is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy; linear or branched, C₁-C₄-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; COOH or COOC₁-C₂alkyl, Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and C₁-C₂alkoxy, Z′ is SO₃M; COOH or COOC₁-C₂alkyl, Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 1; 2 or 3, n′ is 0 or 1, n″ is 0 or 1, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, X is hydrogen; SO₃M; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy; linear or branched, C₁-C₄-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; COOH or COOC₁-C₂alkyl, Y is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₄-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₄-alkoxy; linear or branched, C₁-C₄-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; COOH or COOC₁-C₂alkyl, Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and C₁-C₂alkoxy, Z′ is SO₃M; COOH or COOC₁-C₂alkyl, Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 1; 2 or 3, n′ is 0 or 1, n″ is 0 or 1, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and C₁-C₂alkoxy, Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 1; 2 or 3, n′ is 0 or 1, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and C₁-C₂alkoxy, Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 1; 2 or 3, n′ is 0 or 1, m is 0 or 1, m¹ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and C₁-C₂alkoxy, Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 1; 2 or 3, n′ is 0 or 1, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and C₁-C₂alkoxy, Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 1; 2 or 3, n′ is 0 or 1, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺; or

wherein * marks the bond to the bridging group L, Z is NH₂; NH-aryl or NH-aryl, wherein the aryl is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl and C₁-C₂alkoxy, Z₁ is OH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 1; 2 or 3, n′ is 0 or 1, m is 0 or 1, m₁ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺,

wherein * marks the bond to the bridging group L, Z₂ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl, naphthyl and pyridyl or OH, Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl, naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl or linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 0; 1 or 2, n′ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, Z₂ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl, naphthyl and pyridyl or OH, Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent G selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl, naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl or linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 1; 2 or 3, n′ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, Z₂ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; NO₂, Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkyl, phenyl, naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl group may be substituted by at least one substituent elected from the group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; NO₂, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, each n is independently from each other 1; 2 or 3, each M is independently from each other hydrogen; Na⁺ or K⁺;

wherein * marks the bond to the bridging group L, Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; or NO₂, Z₄ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; SO₂CH₂CH₂SO₃H; or NO₂, Z₅ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; NO₂; NH₂; NHC₁-C₂alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH₂, C₁-C₂alkyl, CN or COOH; NHCOC₁-C₂alkyl or NHCOOC₁-C₂alkyl, Z₆ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; or NO₂, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, n is 1 or 2, n′ is 0 or 1, each M is independently from each other hydrogen; Na⁺ or K⁺,

wherein * marks the bond to the bridging group L, Z is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; or NO₂, Z₁ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; or NO₂, Z₂ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; or NO₂, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, m is 0 or 1, m₁ is 0 or 1, n is 0 or 1, each n′ is independently from each other 0; 1 or 2, each M is independently from each other hydrogen; Na⁺ or K⁺,

wherein * marks the bond to the bridging group L, Z is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; or NO₂, Z₁ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; or NO₂, Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; or NO₂, Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; or NO₂, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, U is a moiety of formula

wherein Z₂ and Z₃ have the meanings as defined above, m is 0 or 1, m1 is 0 or 1, n is 0 or 1, n′ is 0; 1 or 2, each M is independently from each other hydrogen; Na⁺ or K⁺,

wherein * marks the bond to the bridging group L, Z is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; or NO₂, Z₁ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; or NO₂, Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; NH₂; or NO₂, Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; or NO₂, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, U is a moiety of formula

wherein Z₂ and Z₃ have the meanings as defined above, m is 0 or 1, m1 is 0 or 1, each n is independently from each other 0; 1 or 2, each M is independently from each other hydrogen; Na⁺ or K⁺,

wherein * marks the bond to the bridging group L, Z is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; NH₂ or NO₂, Z₁ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; or NO₂, Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; NH₂; or NO₂, Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; or NO₂, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, U is a moiety of formula

wherein Z₂ and Z₃ have the meanings as defined above, m is 0 or 1, m1 is 0 or 1, n is 1; 2 or 3, n′ is 0; 1 or 2, each M is independently from each other hydrogen; Na⁺ or K⁺,

wherein * marks the bond to the bridging group L, Z is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; SO₂CH₂CH₂SO₃H; NH₂ or NO₂, Z₁ is linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; or NO₂, Z₃ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; NH₂; or NO₂, Z₄ is hydrogen; linear or branched, unsubstituted C₁-C₂-alkyl; linear or branched C₁-C₂-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy, phenyl, naphthyl and pyridyl; linear or branched, unsubstituted C₁-C₂-alkoxy or linear or branched, C₁-C₂-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; OH; or NO₂, G is a direct bond; COOC₁-C₂alkylene; unsubstituted arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl; unsubstituted C₁-C₂alkylene or C₁-C₂-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, NO₂, SO₃H, —NH₂, carboxyl, carb-C₁-C₂alkoxy, C₁-C₂alkoxy and C₁-C₂alkyl, U is a moiety of formula

wherein Z₂ and Z₃ have the meanings as defined above, m is 0 or 1, m1 is 0 or 1, n is 1; 2 or 3, n′ is 0; 1 or 2, each M is independently from each other hydrogen; Na⁺ or K⁺.
 8. A process according to claim 2 wherein D is a radical of formulae (XXXIII)-(XXXV):

wherein * marks the bond to the bridging group.
 9. A process according to claim 2 comprising at least one compound of formula (8) and/or (9)

wherein Me is Zn, AlZ₁, Si(IV)-(Z₁)₂ or Ti(IV)-(Z₁)₂, wherein Z₁ is chloride, fluorine, bromine or hydroxyl, each Q₁ is independently of each other a sulfo or carboxyl group; or a radical of the formula —SO₂X₂—R₁—X₃ ⁺; —O—R₁—X₃ ⁺ or —(CH₂)_(t)—Y₁ ⁺, wherein R₁ is a branched or unbranched C₁-C₄alkylene; 1,3-phenylene or 1,4-phenylene, X₂ is —NH— or —N(C₁-C₄alkyl)-, X₃ ⁺ is a group of the formula

or, in the case where R₁=C₁-C₄alkylene, also a group of the formula

Y₁ ⁺ is a group of the formula

t is 0 or 1, wherein the above formulae R₂ and R₃ independently of one another are C₁-C₆alkyl, R₄ is C₁-C₄alkyl; pentyl; hexyl or NR₇R₈, R₅ and R₆ independently of one another are C₁-C₄alkyl, R₇ and R₈ independently of one another are hydrogen or C₁-C₄alkyl, R₉ and R₁₀ independently of one another are unsubstituted C₁-C₄alkyl or C₁-C₄alkyl substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl, u is from 1 to 6, A₁ is a unit which completes an pyrrole-; imidazol-; pyridine-; pyrazine-; pyrimidine-; pyridazine-ring, and B₁ is a unit which completes a morpholino-; pyrrolidine-; piperazine- or piperidine-ring, each Q₂ is independently from each other hydroxyl; C₁-C₁₀alkyl; branched C₃-C₁₀alkyl; C₂-C₁₀alkenyl; branched C₃-C₁₀alkenyl and mixtures thereof; C₁-C₁₀alkoxy; a sulfo or carboxyl radical; a radical of the formula

 a branched alkoxy radical of the formula

 an alkylethyleneoxy unit of the formula -(T₁)_(d)-(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of the formula COOR₁₈, in which B₂ is hydrogen; hydroxyl; C₁-C₁₈alkyl; C₁-C₁₈alkoxy; —CO₂H; —CH₂COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁; —PO₃ ²⁻M₁; —OPO₃ ²⁻M₁; and mixtures thereof, B₃ is hydrogen; hydroxyl; —COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁ or C₁-C₄alkoxy, M₁ is hydrogen; alkalimetal-ion or an ammonium ion, T₁ is —O— or —NH—, X₁ and X₄ independently of one another are —O—; —NH— or —N(C₁-C₄alkyl)-, R₁₁ and R₁₂ independently of one another are hydrogen; a sulfo group and salts thereof; a carboxyl group and salts thereof or a hydroxyl group; at least one of the radicals R₁₁ and R₁₂ being a sulfo or carboxyl group or salts thereof, Y₂ is —O—; —S—; —NH— or —N(C₁-C₄alkyl)-, R₁₃ and R₁₄ independently of one another other are hydrogen; C₁-C₄alkyl; hydroxy-C₁-C₄alkyl; cyano-C₁-C₄alkyl; sulfo-C₁-C₄alkyl; carboxy or halogen-C₁-C₄alkyl; unsubstituted phenyl or phenyl substituted by at least one substitutent selected from the group consisting of halogen, C₁-C₄alkyl and C₁-C₄alkoxy; sulfo or carboxyl or R₁₃ and R₁₄ together with the nitrogen atom to which they are bonded form morpholino, piperazine or piperidine ring, R₁₅ and R₁₆ independently of one another are C₁-C₄alkyl or aryl-C₁-C₄alkyl radicals, R₁₇ is hydrogen; an unsubstituted C₁-C₄alkyl or C₁-C₄alkyl substituted by at least one substitutent selected from the group consisting of halogen, hydroxyl, cyano, SO₃H, —NH₂, phenyl, carboxyl, carb-C₁-C₄alkoxy or C₁-C₆alkoxy, R₁₈ is C₁-C₁₀alkyl; branched C₃-C₁₀alkyl; C₁-C₁₀alkenyl or branched C₃-C₁₀alkenyl; C₃-C₂₂glycol; C₁-C₁₀alkoxy; branched C₃-C₁₀alkoxy; and mixtures thereof, M is hydrogen; Na⁺; K⁺ or an ammonium ion, Z₂ ⁻ a is a alkanolate; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; R₀SO₃ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻; citrate ion; tartrate ion or oxalate ion, wherein R₀ is hydrogen; or unsubstituted C₁-C₁₈alkyl; or C₁-C₁₈alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy, phenyl, naphthyl and pyridyl; unsubstituted aryl or aryl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy and C₁-C₄-alkyl, a is 0 or 1, b is from 0 to 6, c is from 0 to 100, d is 0; or 1, e is from 0 to 22, v is an integer from 2 to 12, w is 0 or 1, and A⁻ is an organic or inorganic anion, and s is equal to r₂, r₃, r₄ and r₅ in cases of monovalent anions A⁻ and is less than or equal to r₂, r₃, r₄ and r₅ in cases of polyvalent anions, it being necessary for A_(s) ⁻ to compensate the positive charge; where, when r₂, r₃, r₄ and r₅≠1, the radicals Q₁ can be identical or different, each L is independently from each other a direct bond; —SO₂—; —O—; —OR₁₉—; —OR₁₉O—; —OR₁₉N(R₂₀)—; —N(R₂₀)—; —(CH₂CH₂O—)_(n)—; —C(O)—; —C(O)N(R₂₀)—; —N(R₂₀)C(O)—; —OC(O)—; —C(O)O—; —S—; unsubstituted, linear or branched C₁-C₁₈alkylene; linear or branched C₁-C₁₈alkylene, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; unsubstituted C₅-C₁₈arylene; C₅-C₁₈arylene, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted, linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl; linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; unsubstituted, linear or branched C₅-C₁₁arylene-C₁-C₁₈alkyl or linear or branched C₅-C₁₈arylene-C₁-C₁₈alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl, wherein R₁₉ is unsubstituted, linear or branched C₁-C₁₈alkylene; linear or branched C₁-C₁₈alkylene, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; unsubstituted C₅-C₁₈arylene; C₅-C₁₈arylene, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted, linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl; linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; unsubstituted, linear or branched C₅-C₁₈arylene-C₁-C₁₈alkyl or linear or branched C₅-C₁₈arylene-C₁-C₁₈alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl, R₂₀ is unsubstituted, linear or branched C₁-C₁₈alkyl; linear or branched C₁-C₁₈alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; unsubstituted C₅-C₁₈aryl; C₅-C₁₈aryl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted, linear or branched C₁-C₁₈alkoxy or linear or branched C₁-C₁₈alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl, N is 1; 2; 3 or 4, each D is independently from each other a dyestuff radical of formula (I), (II), (III), (IV), (V), (VI), (VII), (VII), (IX), (X), (XI), (XII), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII), (XIX), (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV), (XXVI), (XXVIIa), (XXVIIb), (XXVIIc), (XXVIId), (XXVIII), (XXIX), (XXX), (XXXI), (XXXII), (XXXIII), (XXXIV), (XXXV), (I′), (II′), (III′), (IV′), (V′), (VI′), (VIIa′), (VIIb′), (VIII′), (IX′), (X′), (XI′), (XII′), (XIII′), (XIV′), (XV′), (XVI′), (XVII′), (XVIII′), (XIX′), (XX′), (XXI′), (XXVIIa′), (XXVIIb′), (XXVIIc′), (XXVIId′), (XXVIII′), (XXIX′), (XXX′), (XXXI′), (XXXII′), r₂ is 0 or 1, r₃ is 0 or 1, and r₄ is 0 or
 1. 10. A shading process according to claim 1, wherein the shading process is part of a laundry washing process.
 11. A shading composition (A) comprising at least one compound of formula (1a) and/or (1b) according to claim
 2. 12. A shading composition (A″) according to claim 11 comprising at least one compound of formula (8) and/or (9).
 13. A shading composition according to claim 12 in the form of a granule comprising a) from 2 to 75% by weight (wt-%) of at least one shading composition (A) and/or (A″) as defined in claim 12, based on the total weight of the granulate, b) from 10 to 95 wt-% of at least one further additive, based on the total weight of the granulate, and c) from 0 to 15 wt-% water, based on the total weight of the granulate.
 14. A shading composition according to claim 12 in liquid form comprising (a) 0.01-95 wt-%, of at least one shading composition (A) and/or (A″) as defined in claim 12, based on the total weight of the liquid formulation, (b) 5-99.99 wt-%, based on the total weight of the liquid formulation, of at least one organic solvent and (c) 0-10 wt-%, based on the total weight of the liquid formulation, of at least one further additive.
 15. A washing agent formulation (WAF) comprising I) from 5 to 70 wt-% A) of at least one anionic surfactant and/or B) at least one non-ionic surfactant, based on the total weight of the washing agent formulation, II) from 5 to 60 wt-% C) of at least one builder substance, based on the total weight of the washing agent formulation, III) from 0 to 30 wt-% D) of at least one peroxide and, optionally, at least one activator and/or at least one catalyst, based on the total weight of the washing agent formulation, and IV) from 0.001 to 1 wt-% E) of granulate as defined in claim 13, based on the total weight of the washing agent formulation, V) from 0 to 60 wt-% F) of at least one further additive, based on the total weight of the washing agent formulation, and VI) from 0 to 5 wt-% G) water, based on the total weight of the washing agent formulation.
 16. A fabric softener formulation (FSF) comprising (a) at least one shading composition (A) and/or (A″) according to claim 12, and (b) at least one fabric softener.
 17. A Zn-, Ca-, Mg-, Na-, K-, Al, Si-, Ti-, Ge-, Ga-, Zr-, In- or Sn-phthalocyanine compound according to claim 1 to which at least one dyestuff is attached through covalent bonding.
 18. A compound of formula (1a) and/or formula (1b) according to claim 17

wherein PC is the phthalocyanine ring system, Me is Zn; Ca; Mg; Na; K; Al-Z₁; Si(IV)-(Z₁)₂; Ti(IV)-(Z₁)₂; Ge(IV)-(Z₁)₂; Ga(III)-Z₁; Zr(IV)-(Z₁)₂; In(III)-Z₁ or Sn(IV)-(Z₁)₂, Z₁ is an alkanolate ion; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; R₀SO₃ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻; citrate ion; tartrate ion or oxalate ion, wherein R₀ is hydrogen; or unsubstituted C₁-C₁₈alkyl; or C₁-C₁₈alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy, phenyl, naphthyl and pyridyl; unsubstituted aryl or aryl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy and C₁-C₄-alkyl, r is 0; 1; 2; 3 or 4, r′ is 1; 2; 3 or 4, each Q₁ is independently of each other a sulfo or carboxyl group or a radical of the formula —SO₂X₂—R₁—X₃ ⁺; —O—R₁—X₃ ⁺ or —(CH₂)_(t)—Y₁ ⁺, in which R₁ is a branched or unbranched C₁-C₈alkylene; 1,3-phenylene or 1,4-phenylene, X₂ is —NH— or —N(C₁-C₅alkyl)-, X₃ ⁺ is a group of the formula

or, in the case where R₁=C₁-C₈alkylene, also a group of the formula

Y₁ ⁺ is a group of the formula

t is 0 or 1, wherein the above formulae R₂ and R₃ independently of one another are C₁-C₆alkyl, R₄ is C₁-C₆alkyl; C₅-C₇cycloalkyl or NR₇R₈, R₅ and R₆ independently of one another are C₁-C₅alkyl, R₇ and R₈ independently of one another are hydrogen or C₁-C₅alkyl, R₉ and R₁₀ independently of one another are unsubstituted C₁-C₆alkyl or C₁-C₆alkyl substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy, phenyl, naphthyl and pyridyl, u is from 1 to 6, A₁ is a unit which completes an aromatic 5- to 7-membered nitrogen heterocycle, which may where appropriate also contain one or two further nitrogen atoms as ring members, and B₁ is a unit which completes a saturated 5- to 7-membered nitrogen heterocycle, which may where appropriate also contain 1 to 2 nitrogen, oxygen and/or sulfur atoms as ring members, each Q′ is independently from each other a moiety of formula -L-D, wherein L is a direct bond or a bridging group and D is the radical of a dyestuff, each Q₂ is independently from each other hydroxyl; C₁-C₂₂alkyl; branched C₃-C₂₂alkyl; C₂-C₂₂alkenyl; branched C₃-C₂₂alkenyl and mixtures thereof; C₁-C₂₂alkoxy; a sulfo or carboxyl radical; a radical of the formula

 a branched alkoxy radical of the formula

 an alkylethyleneoxy unit of the formula -(T₁)_(d)-(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of the formula COOR₁₈, wherein B₂ is hydrogen; hydroxyl; C₁-C₃₀alkyl; C₁-C₃₀alkoxy; —CO₂H; —CH₂COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁; —PO₃ ²⁻M₁; —OPO₃ ²⁻M₁; and mixtures thereof, B₃ is hydrogen; hydroxyl; —COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁ or C₁-C₆alkoxy, M₁ is a water-soluble cation, T₁ is —O— or —NH—, X₁ and X₄ independently of one another are —O—; —NH— or —N(C₁-C₅alkyl)-, R₁₁ and R₁₂ independently of one another are hydrogen; a sulfo group and salts thereof; a carboxyl group and salts thereof or a hydroxyl group; at least one of the radicals R₁₁ and R₁₂ being a sulfo or carboxyl group or salts thereof, Y₂ is —O—; —S—; —NH— or —N(C₁-C₅alkyl)-, R₁₃ and R₁₄ independently of one another other are hydrogen; C₁-C₆alkyl; hydroxy-C₁-C₆alkyl; cyano-C₁-C₆alkyl; sulfo-C₁-C₆alkyl; carboxy or halo-C₁-C₆alkyl; unsubstituted phenyl or phenyl substituted by at least one substituent selected from the group consisting of halogen, C₁-C₄alkyl, C₁-C₄alkoxy, sulfo or by carboxy; or R₁₈ and R₁₉, together with the nitrogen atom to which they are bonded, form a saturated 5- or 6-membered heterocyclic ring that may in addition contain a further nitrogen atom or an oxygen atom as ring member, R₁₅ and R₁₆ independently of one another are C₁-C₆alkyl or aryl-C₁-C₆alkyl radicals, R₁₇ is hydrogen; an unsubstituted C₁-C₆alkyl or C₁-C₆alkyl substituted by at least one substituent selected from the group consisting of halogen, hydroxyl, cyano, SO₃H, —NH₂, phenyl, carboxyl, carb-C₁-C₆alkoxy and C₁-C₆alkoxy, R₁₈ is C₁-C₂₂alkyl; branched C₃-C₂₂alkyl; C₁-C₂₂alkenyl or branched C₃-C₂₂alkenyl; C₃-C₂₂glycol; C₁-C₂₂alkoxy; branched C₃-C₂₂alkoxy; and mixtures thereof, M is hydrogen; or an alkali metal ion or ammonium ion, Z₂ is a is an alkanolate ion; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; R₀SO₃ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻; citrate ion; tartrate ion or oxalate ion, wherein R₀ is hydrogen; or unsubstituted C₁-C₁₈alkyl; or C₁-C₁₈alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy, phenyl, naphthyl and pyridyl; unsubstituted aryl or aryl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy and C₁-C₄-alkyl, a is 0 or 1, bis from 0 to 6, c is from 0 to 100, d is 0 or 1, e is from 0 to 22, v is an integer from 2 to 12, w is 0 or 1, and A⁻ is an organic or inorganic anion, and s is equal to r in cases of monovalent anions A⁻ and is ≦r in cases of polyvalent anions, it being necessary for A_(s) ⁻ to compensate the positive charge; where, when r≠1, the radicals Q₁ can be identical or different, and where the phthalocyanine ring system may also comprise further solubilising groups.
 19. Compounds of (8) and (9) according to claim 17

wherein Me is Zn, AlZ₁, Si(IV)-(Z₁)₂ or Ti(IV)-(Z₁)₂, wherein Z₁ is chloride, fluorine, bromine or hydroxyl, each Q₁ is independently of each other a sulfo or carboxyl group; or a radical of the formula —SO₂X₂—R₁—X₃ ⁺; —O—R₁—X₃ ⁺ or —(CH₂)_(t)—Y₁ ⁺, wherein R₁ is a branched or unbranched C₁-C₄alkylene; 1,3-phenylene or 1,4-phenylene, X₂ is —NH— or —N(C₁-C₄alkyl)-, X₃ ⁺ is a group of the formula

or, in the case where R₁=C₁-C₄alkylene, also a group of the formula

Y₁ ⁺ is a group of the formula

t is 0 or 1, wherein the above formulae R₂ and R₃ independently of one another are C₁-C₆alkyl, R₄ is C₁-C₄alkyl; pentyl; hexyl or NR₇R₈, R₅ and R₆ independently of one another are C₁-C₄alkyl, R₇ and R₈ independently of one another are hydrogen or C₁-C₄alkyl, R₉ and R₁₀ independently of one another are unsubstituted C₁-C₄alkyl or C₁-C₄alkyl substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl, u is from 1 to 6, A₁ is a unit which completes an pyrrole-; imidazol-; pyridine-; pyrazine-; pyrimidine-; pyridazine-ring, and B₁ is a unit which completes a morpholino-; pyrrolidine-; piperazine- or piperidine-ring, each Q₂ is independently from each other hydroxyl; C₁-C₁₀alkyl; branched C₃-C₁₀alkyl; C₂-C₁₀alkenyl; branched C₃-C₁₀alkenyl and mixtures thereof; C₁-C₁₀alkoxy; a sulfo or carboxyl radical; a radical of the formula

 a branched alkoxy radical of the formula

 an alkylethyleneoxy unit of the formula -(T₁)_(d)-(CH₂)_(b)(OCH₂CH₂)_(a)—B₃ or an ester of the formula COOR₁₈, wherein B₂ is hydrogen; hydroxyl; C₁-C₁₈alkyl; C₁-C₁₈alkoxy; —CO₂H; —CH₂COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁; —PO₃ ²⁻M₁; —OPO₃ ²⁻M₁; and mixtures thereof, B₃ is hydrogen; hydroxyl; —COOH; —SO₃ ⁻M₁; —OSO₃ ⁻M₁ or C₁-C₄alkoxy, M₁ is hydrogen; alkalimetal-ion or an ammonium ion, T₁ is —O— or —NH—, X₁ and X₄ independently of one another are —O—; —NH— or —N(C₁-C₄alkyl)-, R₁₁ and R₁₂ independently of one another are hydrogen; a sulfo group and salts thereof; a carboxyl group and salts thereof or a hydroxyl group; at least one of the radicals R₁₁ and R₁₂ being a sulfo or carboxyl group or salts thereof, Y₂ is —O—; —S—; —NH— or —N(C₁-C₄alkyl)-, R₁₃ and R₁₄ independently of one another other are hydrogen; C₁-C₄alkyl; hydroxy-C₁-C₄alkyl; cyano-C₁-C₄alkyl; sulfo-C₁-C₄alkyl; carboxy or halogen-C₁-C₄alkyl; unsubstituted phenyl or phenyl substituted by at least one substitutent selected from the group consisting of halogen, C₁-C₄alkyl and C₁-C₄alkoxy; sulfo or carboxyl or R₁₃ and R₁₄ together with the nitrogen atom to which they are bonded form a form morpholino, piperazine or piperidine ring, R₁₅ and R₁₆ independently of one another are C₁-C₄alkyl or aryl-C₁-C₄alkyl radicals, R₁₇ is hydrogen; an unsubstituted C₁-C₄alkyl or C₁-C₄alkyl substituted by at least one substitutent selected from the group consisting of halogen, hydroxyl, cyano, SO₃H, —NH₂, phenyl, carboxyl, carb-C₁-C₄alkoxy or C₁-C₆alkoxy, R₁₈ is C₁-C₁₀alkyl; branched C₃-C₁₀alkyl; C₁-C₁₀alkenyl or branched C₃-C₁₀alkenyl; C₃-C₂₂glycol; C₁-C₁₀alkoxy; branched C₃-C₁₀alkoxy; and mixtures thereof, M is hydrogen; Na⁺; K⁺ or an ammonium ion, Z₂ ⁻ a is a alkanolate; a hydroxyl ion; R₀COO⁻; ClO₄ ⁻; BF₄ ⁻; PF₆ ⁻; R₀SO₃ ⁻; SO₄ ²⁻; NO₃ ⁻; F⁻; Cl⁻; Br⁻; I⁻; citrate ion; tartrate ion or oxalate ion, wherein R₀ is hydrogen; or unsubstituted C₁-C₁₈alkyl; or C₁-C₁₈alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy, phenyl, naphthyl and pyridyl; unsubstituted aryl or aryl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, SO₃H, —NH₂, carb-C₁-C₆alkoxy, C₁-C₆alkoxy and C₁-C₄-alkyl, a is 0 or 1, b is from 0 to 6, c is from 0 to 100, d is 0; or 1, e is from 0 to 22, v is an integer from 2 to 12, w is 0 or 1, and A⁻ is an organic or inorganic anion, and is equal to r₂, r₃, r₄ and r₅ in cases of monovalent anions A⁻ and is ≦r₂, r₃, r₄ and r₅ in cases of polyvalent anions, it being necessary for A_(s) ⁻ to compensate the positive charge; where, when r₂, r₃, r₄ and r₅≠1, the radicals Q₁ can be identical or different, each L is independently from each other a direct bond; —SO₂—; —O—; —OR₁₉—; —OR₁₉O—; —OR₁₉N(R₂₀)—; —N(R₂₀)—; —(CH₂CH₂O—)_(n)—; —C(O)—; —C(O)N(R₂₀)—; —N(R₂₀)C(O)—; —OC(O)—; —C(O)O—; —S—; unsubstituted, linear or branched C₁-C₁₈alkylene; linear or branched C₁-C₁₈alkylene, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; unsubstituted C₅-C₁₈arylene; C₅-C₁₈arylene, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted, linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl; linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; unsubstituted, linear or branched C₅-C₁₈arylene-C₁-C₁₈alkyl or linear or branched C₅-C₁₈arylene-C₁-C₁₈alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl, wherein R₁₉ is unsubstituted, linear or branched C₁-C₁₈alkylene; linear or branched C₁-C₁₈alkylene, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; unsubstituted C₅-C₁₈arylene; C₅-C₁₈arylene, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted, linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl; linear or branched C₁-C₁₈alkylene-C₅-C₁₈aryl, which is substituted by at least one substituent G selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl; unsubstituted, linear or branched C₅-C₁₈arylene-C₁-C₁₈alkyl or linear or branched C₅-C₁₈arylene-C₁-C₁₈alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl, R₂₀ is unsubstituted, linear or branched C₁-C₁₈alkyl; linear or branched C₁-C₁₈alkyl, which is substituted by at least one substituent c selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy, phenyl, naphthyl and pyridyl; unsubstituted C₅-C₁₈aryl; C₅-C₁₈aryl, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkoxy and C₁-C₄alkyl; unsubstituted, linear or branched C₁-C₁₈alkoxy or linear or branched C₁-C₁₈alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxyl, cyano, SO₃H, —NH₂, carboxyl, carb-C₁-C₄alkoxy, C₁-C₄alkyl, phenyl, naphthyl and pyridyl, N is 1; 2; 3 or 4, each D is independently from each other a dyestuff radical of formula (I), (II), (III), (IV), (V), (VI), (VII), (VII), (IX), (X), (XI), (XII), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII), (XIX), (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV), (XXVI), (XXVIIa), (XXVIIb), (XXVIIc), (XXVIId), (XXVIII), (XXIX), (XXX), (XXXI), (XXXII), (XXXIII), (XXXIV), (XXXV), (I′), (II′), (III′), (IV′), (V′), (VI′), (VIIa′), (VIIb′), (VIII′), (IX′), (X′), (XI′), (XII′), (XIII′), (XIV′), (XV′), (XVI′), (XVII′), (XVIII′), (XIX′), (XX′), (XXI′), (XXVIIa′), (XXVIIb′), (XXVIIc′), (XXVIId′), (XXVIII′), (XXIX′), (XXX′), (XXXI′), (XXXII′), r₂ is 0 or 1, r₃ is 0 or 1, and r₄ is 0 or
 1. 20. A process for producing compounds according to claim 17

wherein X and X′ is a leaving group and all other substituents have the meaning as defined in claim
 17. 21. A shading composition according to claim 12 in liquid form comprising (a) 1-80 wt-%, of at least one shading composition (A) and/or (A″), based on the total weight of the liquid formulation, (b) 20-99 wt-%, based on the total weight of the liquid formulation, of at least one organic solvent and (c) 0-5 wt-%, based on the total weight of the liquid formulation, of at least one further additive.
 22. A shading composition according to claim 21 in liquid form comprising (a) 5-70 wt-% of at least one shading composition (A) and/or (A″), based on the total weight of the liquid formulation, (b) 30-95 wt-%, based on the total weight of the liquid formulation, of at least one organic solvent and (c) 0-2 wt-%, based on the total weight of the liquid formulation, of at least one further additive. 